Substituted fused heterocyclic herbicides

ABSTRACT

The invention relates to certain substituted fused compounds of Formula I ##STR1## which are useful as herbicides, and their agriculturally suitable compositions, as well as methods for their use as general or selective preemergent or postemergent herbicides or as plant growth regulants.

BACKGROUND OF THE INVENTION

This invention relates to certain substituted fused heterocyclic compounds which are useful as herbicides and their agriculturally suitable compositions as well as methods for their use as general or selective preemergent or postemergent herbicides or as plant growth regulants.

New compounds effective for controlling the growth of undesired vegetation are in constant demand. In the most common situation, such compounds are sought to selectively control the growth of weeds in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed growth in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. In other situations, herbicides are desired which will control all plant growth. Examples of areas in which complete control of all vegetation is desired are areas around railraod tracks, storage tanks and industrial storage areas. There are many products commercially available for these purposes, but the search continues for products which are more effective, less costly and environmentally safe.

EP-A-353,902 discloses herbicidal compounds of the formula ##STR2## wherein, inter alia G and G¹ are N and C; and

X, Y and Z are independently CR₇ or N.

Ind. J. Chem. 1980, 19B, 1011-1013 discloses without teaching herbicidal utility compounds of the formula ##STR3##

SUMMARY OF THE INVENTION

This invention comprises compounds of Formula I, agriculturally suitable compositions containing them, and their method-of-use as preemergence and/or postemergence herbicides or plant growth regulants. ##STR4## wherein X is N or CH;

Y is N or CR₈ ;

Z is N, CR⁴ or CR⁵ ;

Q is N, CR⁴ or CR⁵ ;

R is C₁ -C₄ alkyl, C₂ -C₄ alkoxyalkyl, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₃ alkylamino or N(C₁ -C₃ alkyl)(C₁ -C₃ alkyl);

R¹ is H, F, Cl or CH₃ ;

R² is H, halogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy or C₁ -C₃ haloalkoxy;

R³ is H, halogen, C₁ -C₄ alkyl, C₂ -C₄ alkenyl, C₂ -C₄ haloalkyl, C₁ -C₄ haloalkyl, C₃ -C₄ halocycloalkyl, C₂ -C₄ haloalkenyl, C₂ -C₄ haloalkynyl, OR⁶, S(O)_(n) R⁷ or CN;

R⁴ is H, CN, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or halogen;

R⁵ is C₁ -C₄ haloalkyl, C₃ -C₅ halocycloalkyl, C₂ -C₄ haloalkenyl, C₂ -C₄ haloalkynyl, OR⁶, S(O)_(n) R⁷ or halogen;

R⁶ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, C₁ -C₄ haloalkyl, C₂ -C₄ haloalkenyl or C₂ -C₄ haloalkynyl;

R⁷ is C₁ -C₂ alkyl or C₁ -C₂ haloalkyl;

R⁸ is H, CN, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or halogen; and

n is 0, 1 or 2.

and their mono N-oxides and their agriculturally suitable salts, provided that:

(a) when Z is N or CR⁴, then Q is CR⁵ ; and

(b) when Q is N or CR⁴, then Z is CR⁵.

In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight chain or branched alkyl, e.g., methyl, ethyl, n-propyl, isopropyl or the different butyl isomers.

"Alkoxy", "alkenyl" and "alkynyl" analogously also includes straight chain or branched isomers.

"Halogen", either alone or in compound words such as "haloalkyl", means fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples include CF₃, CH₂ CF₃, CH₂ CH₂ F, CF₂ CF₃ and CH₂ CHFCl.

Preferred for reasons including ease of synthesis and/or greater herbicidal efficacy are:

1. Compounds of Formula I wherein

R¹ is H or F; and

R² is H or F.

2. Compounds of Preferred 1 wherein

R³ is F, Cl, Br, C₁ -C₄ haloalkyl, OR⁶, S(O)_(n) R⁷ or CN;

n is 0;

Y is N, CH or C--CN; and their mono N-oxides.

3. Compounds of Preferred 2 wherein

R is C₁ -C₃ alkyl, C₂ -C₃ alkoxyalkyl, C₂ -C₃ alkenyl, C₂ -C₃ alkynyl, C₁ -C₂ alkoxy, C₁ -C₂ alkylthio, C₁ -C₂ alkylamino and N(C₁ -C₂ alkyl)(C₁ -C₂ alkyl);

R⁶ is C₁ -C₃ alkyl, allyl, propargyl, C₁ -C₃ haloalkyl, C₂ -C₃ haloalkenyl.

4. Compounds of Preferred 3 wherein

Z is N, CH or C--CN.

Specifically Preferred for reasons of greatest ease of synthesis and/or greatest herbicidal efficacy are:

2-(difluoromethoxy)-6-methyl-8-[3-(trifluoromethyl)phenyl]quinoxaline;

7-methyl-3-(2,2,2-trifluoroethoxy)-5-[3-(trifluoromethyl)phenyl]-1,2,4-benzotriazine 1-oxide;

7-methyl-3-(2,2,2-trifluoroethoxy)-5-[3-(trifluoromethyl)phenyl]-1,2,4-benzotriazine; and

6-methyl-2-(trifluoromethyl)-8-[3-(trifluoromethyl)phenyl]quinoxaline.

DETAILED DESCRIPTION OF THE INVENTION

Compounds of General Formula I can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 1-10 and Equations 1-5 of of this section as well as by following the specific procedures given in Examples 1-7.

Scheme 1 illustrates the preparation of compounds of General Formula I (where R, R¹, R², R³ X, Y, Z, and Q are defined as above) whereby heterocycles of Formula II where G is bromine or iodine can be coupled with substituted aryl compounds of Formula III where J is a trialkyltin (e.g. Me₃ Sn), trialkylsilyl (e g. Me₃ Si), or a boronic acid (e.g. B(OH)₂) moiety. The coupling is carried out using methods known in the art: Tsuji, J., Organic Synthesis with Palladium Compounds, Springer-Verlag, Berlin, 1980; Negishi, E., Acc. Chem. Res. 1982, 15, 340; Stille, J. K., Angew. Chem. 1986, 98, 504; Yamamoto, A., Yamagi, A., Chem. Pharm. Bull. 1982, 30 , 1731 and 2003; Dondoni, A., Fogagnolo, M., Medici, A., Negrini, E., Synthesis 1987, 185; Dondoni, A., Fantin, G., Fogagnolo, M., Medici A., Pedrini, P., Synthesis 1987, 693; Hoshino, Y., Miyaura, N., Suzuki, A., Bull. Chem. Soc. Jpn. 1988, 61, 3008; Sato, M., Miyaura, N., Suzuki, A., Chem. Lett. 1989, 1405; Miyaura, N., Yanagi, T., Suzuki, A. Synthetic Commun. 1981, 11, 513; Siddiqui, M. A., Snieckus, V., Tetrahedron Lett. 1988, 29, 5463; Sharp, M. J., Cheng, W., Snieckus, V., Tetrahedron Lett. 1987, 28, 5093; Hatanaka, Y., Fukushima, S., Hiyama,, T., Chem. Lett. 1989, 1711; Bailey, T. R., Tetrahedron Lett. 1986, 27, 4407. The coupling of II and III is carried out by heating in the presence of a transition metal catalyst such as tetrakis(triphenylphosphine) palladium(0) or bis(triphenylphoshine)palladium(II) dichloride in a polar or nonpolar aprotic solvent such as acetonitrile or toluene. As shown in Scheme 1, compounds of General Formula I can also be prepared by coupling heterocylic compounds of Formula IV where J is a trialkyltin (e.g. Me₃ Sn), trialkylsilyl (e.g. Me₃ Si), or boronic acid (e.g. B(OH)₂) moiety with aryl halides of Formula V where G is bromine or iodine using the same conditions as described above. ##STR5##

Heterocycles of Formula II can be prepared by the methods summarized in Schemes 2-10 and Equations 1-5. By methods also reported in the above cited art, treatment of heterocycles of Formula II where G is hydrogen, bromine, or iodine with base such as n-butyl lithium followed by quenching with a trialkyltin halide, trialkylsilyl halide, or trialkyl borate gives heterocylic intermediates of Formula IV. Substituted aryl compounds of Formula III and V are either known or readily prepared by methods given in the above references.

As illustrated in Scheme 2, quinolines of Formula IIa and IIb can be prepared by reaction of anilines of Formula VI with substituted acroleins, vinyl ketones, and diketones of Formulas VIIa and VIId where R⁴ and R⁸ are hydrogen or alkyl, R⁵ is haloalkyl, haloalkenyl, haloalkynyl, or halocycloalkyl and R, R¹, and G are as previously defined. By the methods of Skraup (Chem. Ber. 1880, 13, 2086; 1882, 15, 987) and Combs (Compt. rend. 1887, 106, 142; Bull. Soc. Chim. France, 1888, 49, 90), anilines VI can be heated neat with compounds VIIa and VIId followed by treatment with a strong inorganic acid such as sulfuric acid to give IIa and IIb. ##STR6##

Scheme 3 illustrates the synthesis of quinolines IIa and IIc where R⁴ and R⁸ are hydrogen or alkyl, R⁵ is OR⁶, SR⁷ or chlorine, and R, R¹, and G are as defined above. Reaction of anilines of Formula VI with substituted cinnamoyl chlorides of Formula VIIIa with a base such as pyridine with or without a solvent such as methylene chloride or tetrahydrofuran gives cinnamides of Formula VIIIb which can then be treated with an excess of a Lewis acid such as aluminum trichloride using the conditions of Johnston et al (J. Chem. Soc. Perkin I 1972, 1648) to give hydroxyquinolines of Formula VIIIc. Heating VIIIc in thionyl chloride or phosphorous oxychloride gives chloroquinolines IIc. Displacement of the chloro group with R⁶ O⁻ M⁺ or R⁷ S⁻ M⁺ (where M is an alkali or alkaline metal such as sodium, potassium, or lithium and R⁶ and R⁷ are as previously defined) affords quinolines IIa where R⁵ is OR⁶ or SR⁷. Alkylation of VIIIc with R⁶ L (where L is a leaving group such as halogen, e.g. bromine or chlorine) in the presence of a base such as triethylamine or sodium hydroxide can also give IIa where R⁵ is OR⁶. Reaction of VIIIc with phosphorous pentasulfide in a solvent such as pyridine affords mercaptopyridines of Formula VIIId which on alkylation with R⁷ L (L is as described above) gives IIa where R⁵ is SR⁷. Oxidation of IIa where R⁵ is SR⁷ with an oxidizing agent such as meta-chloroperoxybenzoic acid gives quinolines of Formula IIa where R⁵ is S(O)R⁷ or S(O)₂ R⁷. ##STR7##

Quinolines of Formula IIb where R⁴ is alkoxy or halogen and R⁵ is haloalkyl, haloalkenyl, haloalkynyl, or cyclohaloalkyl, R⁸ is hydrogen or alkyl and R, R¹, and G are as defined above can be made from the starting materials VI and cinnamoyl chlorides of Formula VIIIe (Equation 1) using the same chemistry as shown in Scheme 3. ##STR8##

Quinoxalines and pyridopyrazines of Formula IId and IIe where X is CH or N, R⁴ is hydrogen or alkyl, R⁵ is haloalkyl, haloalkenyl, or haloalkynyl, and R, R¹, and G are as previously defined can be made by the procedure shown in Scheme 4. ##STR9## Reduction (e.g. catalylic hydrogenation with palladium on carbon in a solvent such as tetrahydrofuran or ethanol) of nitroanilines and nitropyridinyl amines of Formula VIa gives phenylenediamines and diaminopyridines of Formula VIb. By the methods related to that of Jones et al (Org. Syntheses 1950, 30, 86), Gabriel et al (Chem. Ber. 1907, 40, 4850), and Bottcher (Chem. Ber. 1913, 46, 3084), condensation of VIb with α-diketones and α-ketoaldehydes of Formula IX in a nonpolar or polar protic or aprotic solvent such as ethanol, water, or tetrahydrofuran affords heterocycles IId and IIe.

Schemes 5 and 6 illustrate the syntheses of quinoxalines and pyridopyrazines of Formula IId and IIe where R⁵ is halogen, OR⁶ or SR⁷ and X, R, R¹, R⁴, and G are defined as above. Condensation of compounds of Formula VIb with α-aldo and α-ketoesters of Formula IXa (Scheme 5) by a method similar to that of Hinsberg (Chem. Ber. 1884, 18, 1228) in a polar protic or aprotic solvent such as ethanol, water or tetrahydrofuran gives hydroxyheterocycles of Formula IXb and IXc. Ethyl ester analogs of IXa can also be readily used in this condensation. Treatment of these hydroxyheterocycles with thionyl chloride or phosphorous oxychloride gives the chloroheterocycles IIf and IIg. Displacement of the chloro substituent with R⁶ O⁻ M⁺ or R⁷ S⁻ M⁺ (where M is an alkali or alkaline metal such as sodium, potassium, or lithium) yields compounds IId and IIe (where R⁵ is OR⁶ or SR⁷). ##STR10##

Scheme 6 demonstrates that hydroxyheterocycles IXb and IXc can also be converted to compounds IId and IIe using similar chemistry as that shown in Scheme 3. Preparation of compounds IId and IIe where R⁵ is R⁷ S involve making intermediate mercaptoheterocycles IXd and IXe. ##STR11##

Equation 2 illustrates that compounds IId and IIe where R⁴ is alkoxy and R⁵ is haloalkyl, halocycloalkyl, haloalkenyl, or haloalkynyl and R, R¹, X, and G are as defined above can be made from the starting materials VIb and the α-ketoesters IXf using the same chemistry as that in Schemes 5 and 6. ##STR12##

By a method similar to that reported by Reich et al (J. Med. Chem. 1989, 32, 2474), Scheme 7 summarizes the preparation of benzotriazines and pyridotriazines of Formula IIh where R⁵ is haloalkyl, halocycloalkyl, haloalkenyl, or haloalkynyl and R, R¹, G, and X are as defined above. Reaction of nitrophenyl hyrazines and nitropyridinyl hydrazines of Formula X with an acid chloride of Formula Xa in a polar protic or aprotic solvent such as ethanol or acetonitrile gives hydrazide hydrochlorides of Formula Xb which can undergo catalytic hydrogenation using palladium on carbon or other suitable transition metal catalyst in a polar protic solvent such as ethanol followed by heating to give heterocycles of Formula Xc. Oxidation of Xc with an appropriate oxidizing agent in a suitable medium, e.g. manganese dioxide in aqueous sodium hydroxide or potassium ferricyanide in aqueous ammomium hydroxide, affords IIh. ##STR13##

By the same technique demonstrated in Scheme 7, nitrophenyl hydrazines and nitropyridinyl hydrazines of Formula Xd (Equation 3) can be converted to heterocycles of Formula IIj which are regioisomeric with IIh. ##STR14##

Scheme 8 illustrates the preparation of benzotriazines and pyridotriazines of Formula IIh and their N-oxides IIk and IIl where R⁵ is halogen, OR⁶, or SR⁷ and R, R¹, X, and G are as previously defined. Using the conditions of Wolf et al (J. Org. Chem. 1954, 76, 3551), reaction of VIa with cyanamide in an acid medium such as a mixture of concentrated hydrochloric and acetic acid (extremely exothermic) followed by heating with aqueous base, e.g. sodium hydroxide, provides aminoheterocyclic N-oxides of Formula Xd. Diazotization with sodium nitrite in aqueous sulfuric acid gives hydroxyheterocycles Xe and diazotization in concentrated hydrochloric acid yields chloroheterocycles IIk. By chemistry previously discussed in Scheme 3, IIl can be obtained from both Xe and IIk. Reduction of the N-oxides IIl, e.g. catalytic hydrogenation over palladium, afford IIh. N-oxides IIl can also be coupled directly with III to give N-oxides of I. ##STR15##

Regioisomeric benzotriazines and pyridotriazines of Formula IIj (Equation 4) and their N-oxides where R⁵ is halogen, OR⁶, or SR⁷ and R, R¹, G, and X are as defined previously, can be obtained by starting with nitroanilines and nitropyridinylamines of Formula Xg and applying the chemistry shown in Scheme 8. ##STR16##

By the methods illustrated in Scheme 3, compounds Xe (Scheme 8) can be converted to compounds of Formula IIl as shown in Equation 5. ##STR17##

Scheme 9 demonstrates the Synthesis of heterocycles of Formula IIm and IIn (where R⁵ is haloalkyl, halocycloalkyl, haloalkenyl, or haloalkynyl and other groups defined as indicated above) from amino compounds XI and anhydrides of Formula XIa. The chemistry is related to that described in previous schemes. Hydrogenolysis e.g. catalytic using palladium on carbon, or displacement with R⁸⁻ M⁺ (where R⁸ is alkoxy, CN, or alkyl) of the chloro group of IIm affords IIn where R⁸ is hydrogen, alkoxy, CN, or alkyl. ##STR18##

Preparation of compounds of Formula IIo, IIm, and IIn where R⁵ is halogen, OR⁶ or SR⁷ and the remaining groups are as previously defined is shown in Scheme 10. The chemistry in Scheme 10 is similar to that described in previous schemes. ##STR19##

Cinnolines of Formula II where X is CH, Y is CR⁸, Z is CR⁵ and Q is N, (other substituents as previously defined) can be prepared by the methods reviewed by Elderfield (Heterocyclic Compounds, John Wiley & Sons, 1957, Volume 6, Chapter 5) and used in conjunction with procedures provided in the previous schemes.

N-oxides of compounds of Formula I can be made by treating compounds of Formula I with an oxidizing agent such as meta-peroxybenzoic acid in an appropriate solvent such as methylene chloride. Salts of Formula I can also be prepared by treating compounds of Formula I with a suitable acid such as hydrochloric acid.

EXAMPLE 1 Preparation of 3-(trifluoromethyl)phenyltrimethylstannane

To 20.0 g (88.9 mmol) of meta-bromobenzotrifluoride stirring in 200 ml of tetrahydrofuran at -78° C., 61.2 ml of 1.6M n-butyl lithium (97.9 mmol) in hexane was added dropwise. After stirring the reaction 10 minutes at -78° C., 19.5 g (97.8 mmol) of trimethyltin chloride dissolved in 30 ml of tetrahydrofuran was added dropwise and the mixture stirred for 10 minutes at -78° C. before allowing to warm to room temperature. The reaction mixture was quenched with excess saturated sodium bicarbonate and extracted with ethyl acetate (300 ml). The extract was washed with saturated sodium bicarbonate and brine, dried over magnesium sulfate, and evaporated in vacuo to give a crude yield of 20.2 g of the above product, isolated as a oily semi-solid. This aryl stannane was used directly as a crude material in the coupling reactions with heterocycles of Formula II.

EXAMPLE 2

Preparation of 6-Methyl-2-(2,2,2-trifluoroethoxy)-8-[3-(trifluoromethyl)phenyl]quinoline

To 25.0 (134.4 mmol) of 2-bromo-4-methylaniline stirring in 100 ml of pyridine at 0° C., 29.1 g (174.7 mmol) of cinnamoyl chloride was added dropwise. The mixture was allowed to warm to room temperature and stirred as a thick suspension for 1 h. Methylene chloride (400 ml) and excess 5% hydrochloric acid was added. The organic layer was separated, washed with 5% hydrochloric acid (2X), water and brine, dried over magnesium sulfate, and evaporated in vacuo. To the residue, n-butyl chloride was added and a solid filtered and dried to give a 33.8 g yield of N-2-bromo-4-methylphenyl cinnamide, m.p. 148°-149° C. (ethyl acetate).

A mixture of 15.0 g (47.5 mmol) of the above prepared N-2-bromo-4-methylphenyl cinnamide and 18.9 g (142.1 mmol) of aluminum trichloride was heated as a melt at about 100° C. for 1.25 h. The viscous syrup was poured onto ice and the resulting aqueous mixture stirred 10 minutes and extracted with ethyl acetate (400 ml). The organic extract was washed with water, brine, dried over magnesium sulfate, and evaporated in vacuo. To the residue was added n-butyl chloride and 5.5 g of a crude solid (8-bromo-2-hydroxy-6-methylquinoline) was filtered, dried, and taken on directly to the next step without characterization.

A 5.0 g sample of the above solid and 35 ml of phosphorous oxychloride was heated at reflux for 30 minutes. The hot mixture was poured onto excess ice and the resulting aqueous mixture extracted with 300 ml of diethyl ether. The ether extract was separated and washed with water, brine, dried over magnesium sulfate, and evaporated in vacuo to give a dark oil. Silica gel column chromatography (5:1 followed by 3:1 hexane/ethyl acetate) afforded 1.8 g of 8-bromo-2-chloro-6-methylquinoline isolated as a solid, m.p. 107°-108° C. A second lower R_(f) material (1.1 g) was also isolated on chromatography and identified as 2-chloro-6-methylquinoline, m.p. 109°-111° C.

To 0.8 g of 60% sodium hydride (oil dispersion) stirring in 20 ml of tetrahydrofuran at room temperature, 2.5 ml (34.3 mmol) of 2,2,2-trifluoroethanol was added dropwise. An exotherm occurred and to the resulting solution 1.7 g (6.7 mmol) of 8-bromo-2-chloro-6-methylquinoline was added followed by heating at reflux for 7 h. Ethyl acetate (200 ml) and excess water was added and the organic layer separated and washed with water and brine, dried over magnesium sulfate, and evaporated in vacuo to give an oil. Silica gel column chromatography (20:1 followed by 10:1 hexane/ethyl acetate) afforded 1.9 g of 8-bromo-6-methyl-2-(2,2,2-trifluoroethoxy)quinoline, m.p. 61°-62° C.

A mixture of 1.5 g (6.2 mmol) of 8-bromo-6-methyl-2-(2,2,2-trifluoroethoxy)quinoline, 2.3 g of crude 3-(trifluoromethyl)phenyltrimethylstannane (Example 1), and 0.2 g of tetrakis(triphenylphosphine)palladium(O) was heated in 30 ml of toluene at reflux with stirring for 3 hours. Ethyl acetate (200 ml) and excess water was added. The organic layer was separated, washed with water and brine, dried over magnesium sulfate, and evaporated in vacuo to give an oil. Silica gel column chromatography (20:1 followed by 10:1 hexane/ethyl acetate) afforded 0.7 g of product, isolated as an oil. NMR(CDCl₃): ppm 2.55 (s, 3H), 4.71 (q, 2H), 7.15 (d, 1H), 7.5-8.15 (m, 7H).

EXAMPLE 3 Preparation of 6-Methyl-2-(2.2.2-trifluoroethoxy)-8-[3-(trifluoromethyl)phenyl]quinoxaline and 6-Methyl-3-(2,2,2-trifluoroethoxy)-8-[3-(trifluoromethyl)phenyl]quinoxaline

A mixture of (92 mmol) of 2-bromo-4-methyl-6-nitroaniline and catalytic amount of 10% palladium on carbon in 120 ml of tetrahydrofuran was placed on a Paar hydrogenator for 6 h at room temperature at 50-40 psi. The reaction mixture was filtered through celite and to the filtrate was added dropwise 50.0 ml of 50% glyoxylic acid. The resulting suspension was stirred at room temperature overnight, the insoluble material filtered, washed with water and ethyl acetate, and oven dried to yield 8.5 g of a mixture of 8-bromo-2-hydroxy-6-methylquinoxaline and 8-bromo-3-hydroxy-6-methylquinoxaline.

A 5.0 g (20.9 mmol) sample of the above mixture of 2- and 3-hydroxyquinoxalines was heated in 30 ml of thionyl chloride containing a few drops of dimethylformamide. The reaction was heated at reflux for 1.5 h and the resulting solution, which gradually formed on heating, was poured carefully onto ice. The aqueous was extracted with ethyl acetate (250 ml) and the separated organic layer washed with water (2X) and brine, dried over magnesium sulfate, and yellow solid residue. Hexane was added and the mixture stirred several minutes before filtering to give,2.1 g of only 8-bromo-3-chloro-6-methylquinoxaline. Evaporating the hexane filtrate to dryness gave another 3.2 g of a crude solid which was roughly a 1:1 mixture of 8-bromo-2-chloro-6-methylquinoxaline and 8-bromo-3-chloro-6-methylquinoxaline.

To 0.46 g of 60% sodium hydride (oil dispersion) stirring in 20 ml of tetrahydrofuran, was added dropwise 1.54 ml of 2,2,2-trifluoroethanol followed by the addition of 1.8 g of the above crude mixture of quinoxalines. The reaction mixture was heated at reflux 45 minutes. Glacial acetic acid (2.0 ml) and excess water was added and the aqueous mixture extracted with ethyl acetate. The separated organic layer was washed with water, saturated sodium bicarbonate and brine, dried over magnesium sulfate, and evaporated in vacuo to give 2.4 g of an oily solid residue which was taken on directly to the next step.

A stirred mixture of 2.4 g of the above oily solid residue, 4.5 g of crude 3-(trifluoromethyl)-phenyltrimethylstannane (Example 1), and 0.2 g of tetrakis(triphenylphosphine)palladium(0) was heated in 30 ml of toluene for 4 h. The reaction mixture was concentrated to dryness in vacuo and the residue flash chromatographed on silica gel (40:1 hexane/ethyl acetate) to give 0.7 g of 6-methyl-3-(2,2,2-trifluoroethoxy)-8-[3-(trifluoromethyl)phenyl]quinoxaline (first to elute, m.p. 114°-117° C.) and 0.8 g of 6-methyl-2-(2,2,2-trifluoroethoxy)-8-[3-(trifluoromethyl) phenyl]-quinoxaline (m.p. 46°-48° C.).

EXAMPLE 4 Preparation of 2-Methoxy-6-methyl-8-[3-(trifluoromethyl)phenyl]quinoxaline and 3-Methoxy-6-methyl-8-[3-(trifluoromethyl)phenylquinoxaline

To 2.3 g of a crude sample mixture of 8-bromo-2-chloro-6-methylquinoxaline and 8-bromo-3-chloro-6-methylquinoxaline (prepared as in Example 3) stirring in 20 ml of methanol, 6.3 ml of a 25 weight % of sodium methoxide in methanol was added and the mixture heated at reflux for 1 h. Glacial acetic acid (3.0 ml), 200 ml of ethyl acetate, and excess water was added. The separated organic layer was washed with saturated sodium bicarbonate, brine, dried over magnesium sulfate, and evaporated in vacuo to give 2.0 g of an oily solid residue which was taken on directly to the next step.

A stirred mixture of the above oily solid residue, 3.2 g of crude 3-(trifluoromethyl)phenyltrimethylstannane (Example 1), and 0.2 g of tetrakis(triphenylphosphine)palladium(0) were heated in 35 ml of toluene at reflux for 8 h. In vacuo, the reaction mixture was evaporated to dryness and the residue flash chromatographed on silica gel (1:1 hexane/n-butyl chloride followed by straight n-butyl chloride) to give 0.4 g of 3-methoxy-5-methyl-8-[3-(trifluoromethyl)phenyl]quinoxaline (first product isomer to elute, m.p. 141°-142° C.) and 0.5 g of 2-methoxy-5-methyl-8-[3-(trifluoromethyl)phenyl]quinoxaline(m.p. 119°-121° C.).

EXAMPLE 5 Preparation of 2-(Difluoromethoxy)-6-methyl-8-[3-(trifluoromethyl)phenyl]-quinoxaline and 3-(Difluoromethoxy)-6-methyl-8-[3-(trifluoromethyl)-phenyl]quinoxaline

To a suspension of 5.0 g (20.9 mmol) of the above isomer mixture of 8-bromo-2-hydroxy-6-methylquinoxaline and 8-bromo-3-hydroxy-6-methylquinoxaline (prepared as in Example 3) and 9.0 g (27.1 mmol) of tetra-n-butylammonium bromide stirring in 150 ml of dioxane, 20 g (250.0 mmol) of 50% aqueous sodium hydroxide were added. The reaction mixture was placed under an atmosphere of chlorodifluoromethane (Freon-22®) whereby slight pressure was maintained by having a balloon over the reaction flask. A slow exotherm occurred and the mixture stirred 4 h. Excess water and 300 ml of diethyl ether were added. The separated organic extract was washed with water, brine, dried over magnesium sulfate, and evaporated in vacuo to give an oil residue which quickly solidified. Hexane was added, the mixture stirred several minutes, and filtered to give 3.1 g of 8-bromo-3-difluoromethoxy-6-methylquinoxaline. Evaporating the filtrate gave 2.5 g of a crude isomer mixture of 8-bromo-2-difluoromethoxy-6-methylquinoxaline and 8-bromo-3-difluoromethoxy-6-methylquinoxaline.

A stirred mixture of 1.5 g (5.2 mmol) of the above 2- and 3-difluoromethoxyquinoxaline isomer mixture, 4.0 g of crude 3-(trifluoromethyl)phenyltrimethylstannane (Example 1), and 0.2 g of tetrakis(triphenylphosphine)palladium(0) was heated at reflux for 16 h. The reaction mixture was evaporated in vacuo and the residue flash chromatographed on silica gel (9:1 followed by 1:1 hexane/n-butyl chloride) to afford 0.51 g of 3-(difluoromethoxy)-6-methyl-8-[3-(trifluoromethyl)-phenyl]quinoxaline (first product isomer to elute, m.p. 105°-106° C.) and 0.4 g of 2-(difluoromethoxy)-6-methyl-8-[3-(trifluoromethyl)phenyl]quinoxaline (m.p. 103°-104° C.).

EXAMPLE 6 Preparation of 6-Methyl-2-(trifluoromethyl)-8-[3-(trifluoromethyl)phenyl]quinoxaline and 6-Methyl-3-(trifluoromethyl-8-[3-(trifluoroomethyl)phenyl]quinoxaline

A mixture of 20.0 9 (B6.6 mmol) of 2-bromo-4-methyl-6-nitroaniline and a catalytic amount of 10% palladium on carbon in 100 ml of tetrahydrofuran was placed on a Paar hydrogenator at room temperature at 50-40 psi for 6 h. The reaction mixture was filtered through celite which was then washed with ethyl acetate. A total of 300 ml of ethyl acetate was added to the filtrate which was washed with water, brine, dried over magnesium sulfate and evaporated in vacuo to give a dark oily semi-solid. Flash column silica gel chromatography (methylene chloride followed by 2:1 hexane/ethyl acetate) afforded 17.0 g of the main component: 3-bromo-5-methyl-ortho-phenylenediamine. The chromatopgraphed product, which still contained some minor impurities, was used directly in the next step. It was initially an dark oil which solidified.

To 10.0 g (37.0 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone stirring in 50 ml of water, 8.0 g (97.6 mmol) of anhydrous sodium acetate was added and the stirred mixture heated near reflux for 45 minutes followed by stirring at ambient temperature for 30 minutes. A 4.0 g (20.0 mmol) sample of the above phenylenediamine was added and the mixture stirred 2 h. Excess water and 250 ml of ethyl acetate was added and the separated organic extract washed with 5% hydrochloric acid, brine, dried over magnesium sulfate, and evaporated in vacuo to give dark oil. Flash column silica gel chromatography (40:1 followed by 30:1 hexane/ethyl acetate) afforded 4.3 g of a mixture (two close migrating spots) of 8-bromo-6-methyl-2-trifluoromethylquinoxaline and 8-bromo-6-methyl-3-trifluoromethylquinoxaline, isolated as a solid which melted at 69°-71° C.

A stirred mixture of 2.0 g (6.9 mmol) of the above quinoxaline isomers, 4.2 g of crude 3-(trifluoromethyl)phenyltrimethylstannane, and 0.2 g of tetrakis(triphenylphosphine)palladium(0) were heated in 30 ml of toluene for 6 h. Additional stannane (about 0.5 g) and palladium catalyst (0.1 g) were added and the reaction heated another 6 h. The reaction mixture was evaporated in vacuo to dryness and the residue flash chromatographed (4:1 followed by 1:1 hexane/n-butyl chloride followed in turn by 100% n-butyl chloride) to afford 0.2 g of 6-methyl-3-(trifluoromethyl)-8-[3-(trifluoromethyl)-phenyl]quinoxaline (first product isomer to elute, m.p. 93°-94° C.) and 1.08 g of 6-methyl-2-(trifluoromethyl)-8-[3-(trifluoromethyl)phenyl]quinoxaline (m.p. 117°-118° C.).

EXAMPLE 7 7-Methyl-3-(2,2,2-trifluoroethoxy)-5-[3-(trifluoromethyl)phenyl]-1,2,4-benzotriazine-1-oxide and 7-Methyl-3-(2,2,2-trifluoroethoxy)-5-[3-trifluoromethyl)phenyl]- 1,2,4-benzotriazine

To 13.0 g (56.3 mmol) of 2-bromo-4-methyl-6-nitroaniline stirring in a mixture of 25 ml glacial acetic acid and 5 ml of concentrated hydrochloric acid at 80° C., 29.0 g (690.5 mmol) of cyanamide and 25 ml of concentrated hydrochloric acid were added simultaneously, separately, and very slowly. At one point during the addition, a vigorous exotherm occurred and the external heat immediately removed. After the addition, the reaction was heated at reflux for 15 minutes. On cooling to about 50° C., 100 ml of 25% aqueous sodium hydroxide were added dropwise and the mixture heated at reflux 15 minutes. The reaction was cooled to room temperature, the insoluble orange solid filtered and washed with water followed by ethyl acetate to afford 7.4 g of yellow 3-amino-5-bromo-7-methyl-1,2,4-benzotriazine-1-oxide after drying.

Sodium nitrite (7.0 g, 101.4 mmol) was added portionwise to a suspension of 7.0 g (27.5 mmol) of the above aminobenzotriazine-N-oxide stirring in 140 ml of concentrated hydrochloric acid at ambient temperature. The mixture was stirred overnight and heated at 60° C. for 2 h. Excess water and 400 ml of ethyl acetate were added and the separated organic layer washed with water, saturated sodium bicarbonate, brine, and dried over magnesium sulfate. Some insoluble starting aminoheterocycle was present during the extractive workup but was not attempted to be removed. Evaporating the organic extract to dryness in vacuo afforded a crude yellow solid residue which was flash chromatographed on silica gel (4:1 methylene chloride/hexane) to give 2.5 g of 5-bromo-3-chloro-7-methyl-1,2,4-benzotriazine-1-oxide, m.p. 207°-209° C.

To 0.5 g of 60% sodium hydride stirring in 30 ml of tetrahydrofuran, 3.0 ml of 2,2,2-trifluoroethanol was added dropwise at ambient temperature. A solution resulted and 2.0 g (7.29 mmol) of the above 5-bromo-3-chloro-7-methyl-1,2,4-benzotriazine-1-oxide was added and at ambient temperature and the mixture stirred 2 h. Ethyl acetate (200 ml) and excess water were added and the separated organic extract washed with water, brine, and dried over magnesium sulfate. The solvent was removed in vacuo, hexane added to the residue, and the suspended yellow solid filtered and dried to afford 1.7 g of 5-bromo-7-methyl-3-(2,2,2-trifluoroethoxy)-1,2,4-benzotriazine-1-oxide, m.p. 127°-128° C.

A stirred mixture of 1.3 g (3.84 mmol) of the above benzotriazine N-oxide, 1.4 g of crude 3-(trifluoromethyl)phenyltrimethylstannane, and 0.2 g of tetrakis(triphenylphosphine)palladium(0) were heated in 35 ml of toluene at reflux for 4 h. The reaction mixture was evaporated in vacuo to dryness and the residue flashed chromatographed on silica gel (1:1 hexane/n-butyl chloride followed by 100% n-butyl chloride) to give 0.8 g of 7-methyl-3-(2,2,2-trifluoroethoxy)-5-[3-(trifluoromethyl)phenyl]1,2,4-benzotriazine-1-oxide (m.p. 168°-169° C.) and 0.24 g of 7-methyl-3-(2,2,2-trifluoroethoxy)-5-[3-(trifluoromethyl)phenyl]-1,2,4-benzotriazine (m.p. 140°-141°).

Using the procedures outlined in Schemes 1-10, Equations 1-5, and Examples 1-7, the compounds of Tables I-VIII and the Table of Compounds can readily be prepared by one skilled in the art.

                  TABLE I                                                          ______________________________________                                          ##STR20##                     Ia                                              XR         R.sup.1 R.sup.2                                                                         R.sup.3  R.sup.4                                                                             R.sup.5  R.sup.8                             ______________________________________                                         CH Me      H H      CF.sub.3 H    CF.sub.3 H                                   CH Et      H H      CF.sub.3 H    CF.sub.3 H                                   CH n-Pr    H H      CF.sub.3 H    CF.sub.3 H                                   CH Me      H H      OCF.sub.3                                                                               H    CF.sub.3 H                                   CH Et      H H      OCF.sub.3                                                                               H    CF.sub.3 H                                   CH n-Pr    H H      OCF.sub.3                                                                               H    CF.sub.3 H                                   CH Me      H H      OCHF.sub.2                                                                              H    CF.sub.3 H                                   CH Me      H H      OCF.sub.3                                                                               H    OCHF.sub.2                                                                              H                                   CH Me      H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   CH Me      FH       CF.sub.3 H    CF.sub.3 H                                   CH Me      H 6-F    CF.sub.3 H    CF.sub.3 H                                   CH Me      H 4-F    CF.sub.3 H    CF.sub.3 H                                   CH Me      H 2-OMe  CF.sub.3 H    CF.sub.3 H                                   CH Me      H 2-CF.sub.3                                                                            H        H    CF.sub.3 H                                   CH Me      H H      Cl       H    CF.sub.3 H                                   CH Me      H H      Br       H    CF.sub.3 H                                   CH Me      H H      CN       H    CF.sub.3 H                                   CH Et      H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   CH Et      H H      CN       H    CF.sub.3 H                                   CH Me      H H      SCF.sub.3                                                                               H    CF.sub.3 H                                   CH Me      H H      H        H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 H    OCH.sub.2 CF.sub.3                                                                      H                                   CH Me      H H      CF.sub.3 H    SCF.sub.3                                                                               H                                   CH Me      H H      CF.sub.3 H    OMe      H                                   CH Et      H H      CF.sub.3 H    OEt      H                                   CH Me      H H      CF.sub.3 H    OCHMe.sub.2                                                                             H                                   CH Me      H H      CF.sub.3 H    SMe      H                                   CH Me      H H      CF.sub.3 H    CHF.sub.2                                                                               H                                   CH Et      H H      CF.sub.3 H    CHF.sub.2                                                                               H                                   CH Me      H H      OCF.sub.3                                                                               H    CHF.sub.2                                                                               H                                   CH Me      H H      CF.sub.3 H    OCF.sub.2 CHF.sub.2                                                                     H                                   CH Me      H H      CF.sub.3 H    Cl       H                                   CH MeCHCH  H H      CF.sub.3 H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 H    CHCHCF.sub.3                                                                            H                                   CH Me      H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   CH Et      H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   CH MeOCH.sub.2                                                                            H H      CF.sub.3 H    CF.sub.3 H                                   CH Me.sub.2 N                                                                             H H      CF.sub.3 H    CF.sub.3 H                                   CH MeNH    H H      CF.sub.3 H    CF.sub.3 H                                   CH Me      H H      OMe      H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 H    SCHF.sub.2                                                                              H                                   CH Me      H H      CF.sub.3 H    SO.sub.2 CHF.sub.2                                                                      H                                   CH MeO     H H      CF.sub.3 H    CF.sub.3 H                                   CH MeS     H H      CF.sub.3 H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 Me   CF.sub.3 H                                   CH Me      H H      CF.sub.3 CN   CF.sub.3 H                                   CH Me      H H      CF.sub.3 OMe  CF.sub.3 H                                   CH Me      H H      CF.sub.3 Cl   CF.sub.3 H                                   NMe        H H      CF.sub.3 H    CF.sub.3 H                                   NEt        H H      CF.sub.3 H    CF.sub.3 H                                   NMe        H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   NEt        H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   NMe        H H      OCF.sub.3                                                                               H    CF.sub.3 H                                   NMe        H H      OCHF.sub.2                                                                              H    CF.sub.3 H                                   NMe        H H      CN       H    CF.sub.3 H                                   NEt        H H      CN       H    CF.sub.3 H                                   NMe        H H      OCF.sub.3                                                                               H    OCHF.sub.2                                                                              H                                   NMe        H H      CF.sub.3 H    OMe      H                                   NMe        H H      SCF.sub.3                                                                               H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 H    CF.sub.3                                                                               Me                                   CH Me      H H      CF.sub.3 H    CF.sub.3                                                                               OMe                                  CH Me      H H      CF.sub.3 H    CF.sub.3                                                                               Cl                                   CH Me      H H      CF.sub.3 H    CF.sub.3                                                                               CN                                   ______________________________________                                    

                  TABLE II                                                         ______________________________________                                          ##STR21##                     Ib                                              XR         R.sup.1 R.sup.2                                                                         R.sup.3  R.sup.4                                                                             R.sup.5  R.sup.8                             ______________________________________                                         CH Me      H H      CF.sub.3 H    CF.sub.3 H                                   CH Et      H H      CF.sub.3 H    CF.sub.3 H                                   CH n-Pr    H H      CF.sub.3 H    CF.sub.3 H                                   CH Me      H H      OCF.sub.3                                                                               H    CF.sub.3 H                                   CH Et      H H      OCF.sub.3                                                                               H    CF.sub.3 H                                   CH n-Pr    H H      OCF.sub.3                                                                               H    CF.sub.3 H                                   CH Me      H H      OCHF.sub.2                                                                              H    CF.sub.3 H                                   CH Me      H H      OCF.sub.3                                                                               H    OCHF.sub.2                                                                              H                                   CH Me      H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   CH Me      FH       CF.sub.3 H    CF.sub.3 H                                   CH Me      H 6-F    CF.sub.3 H    CF.sub.3 H                                   CH Me      H 4-F    CF.sub.3 H    CF.sub.3 H                                   CH Me      H 2-OMe  CF.sub.3 H    CF.sub.3 H                                   CH Me      H 2-CF.sub.3                                                                            H        H    CF.sub.3 H                                   CH Me      H H      Cl       H    CF.sub.3 H                                   CH Me      H H      Br       H    CF.sub.3 H                                   CH Et      H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   CH Me      H H      CN       H    CF.sub.3 H                                   CH Et      H H      CN       H    CF.sub.3 H                                   CH Me      H H      SCF.sub.3                                                                               H    CF.sub.3 H                                   CH Me      H H      H        H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 H    OCH.sub.2 CF.sub.3                                                                      H                                   CH Me      H H      CF.sub.3 H    SCF.sub.3                                                                               H                                   CH Me      H H      CF.sub.3 H    OMe      H                                   CH Et      H H      CF.sub.3 H    OEt      H                                   CH Me      H H      CF.sub.3 H    OCHMe.sub.2                                                                             H                                   CH Me      H H      CF.sub.3 H    SMe      H                                   CH Me      H H      CF.sub.3 H    CHF.sub.2                                                                               H                                   CH Et      H H      CF.sub.3 H    CHF.sub.2                                                                               H                                   CH Me      H H      OCF.sub.3                                                                               H    CHF.sub.2                                                                               H                                   CH Me      H H      CF.sub.3 H    OCF.sub.2 CHF.sub.2                                                                     H                                   CH Me      H H      CF.sub.3 H    Cl       H                                   CH MeCHCH  H H      CF.sub.3 H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 H    CHCHCF.sub.3                                                                            H                                   CH Me      H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   CH Et      H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   CH MeOCH.sub.2                                                                            H H      CF.sub.3 H    CF.sub.3 H                                   CH Me.sub.2 N                                                                             H H      CF.sub.3 H    CF.sub.3 H                                   CH MeNH    H H      CF.sub.3 H    CF.sub.3 H                                   CH Me      H H      OMe      H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 H    SCHF.sub.2                                                                              H                                   CH Me      H H      CF.sub.3 H    SO.sub.2 CHF.sub.2                                                                      H                                   CH MeO     H H      CF.sub.3 H    CF.sub.3 H                                   CH MeS     H H      CF.sub.3 H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 Me   CF.sub.3 H                                   CH Me      H H      CF.sub.3 CN   CF.sub.3 H                                   CH Me      H H      CF.sub.3 OMe  CF.sub.3 H                                   CH Me      H H      CF.sub.3 Cl   CF.sub.3 H                                   NMe        H H      CF.sub.3 H    CF.sub.3 H                                   NEt        H H      CF.sub.3 H    CF.sub.3 H                                   NMe        H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   NEt        H H      CF.sub.3 H    OCHF.sub.2                                                                              H                                   NMe        H H      OCF.sub.3                                                                               H    CF.sub.3 H                                   NMe        H H      OCHF.sub.2                                                                              H    CF.sub.3 H                                   NMe        H H      CN       H    CF.sub.3 H                                   NEt        H H      CN       H    CF.sub.3 H                                   NMe        H H      OCF.sub.3                                                                               H    OCHF.sub.2                                                                              H                                   NMe        H H      CF.sub.3 H    OMe      H                                   NMe        H H      SCF.sub.3                                                                               H    CF.sub.3 H                                   CH Me      H H      CF.sub.3 H    CF.sub.3                                                                               Me                                   CH Me      H H      CF.sub.3 H    CF.sub.3                                                                               OMe                                  CH Me      H H      CF.sub.3 H    CF.sub.3                                                                               Cl                                   CH Me      H H      CF.sub.3 H    CF.sub.3                                                                               CN                                   ______________________________________                                    

                  TABLE III                                                        ______________________________________                                          ##STR22##                     Ic                                              X    R          R.sup.1                                                                              R.sup.2                                                                              R.sup.3                                                                               R.sup.4                                                                             R.sup.5                                ______________________________________                                         CH   Me         H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Et         H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   n-Pr       H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     H     OCF.sub.3                                                                             H    CF.sub.3                               CH   Et         H     H     OCF.sub.3                                                                             H    CF.sub.3                               CH   n-Pr       H     H     OCF.sub.3                                                                             H    CF.sub.3                               CH   Me         H     H     OCHF.sub.2                                                                            H    CF.sub.3                               CH   Me         H     H     OCF.sub.3                                                                             H    OCHF.sub.2                             CH   Me         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             CH   Me         F     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     6-F   CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     4-F   CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     2-OMe CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     2-CF.sub.3                                                                           H      H    CF.sub.3                               CH   Me         H     H     Cl     H    CF.sub.3                               CH   Et         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             CH   Me         H     H     Br     H    CF.sub.3                               CH   Me         H     H     CN     H    CF.sub.3                               CH   Et         H     H     CN     H    CF.sub.3                               CH   Me         H     H     SCF.sub.3                                                                             H    CF.sub.3                               CH   Me         H     H     H      H    CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              H    OCH.sub.2 CF.sub.3                     CH   Me         H     H     CF.sub.3                                                                              H    SCF.sub.3                              CH   Me         H     H     CF.sub.3                                                                              H    OMe                                    CH   Et         H     H     CF.sub.3                                                                              H    OEt                                    CH   Me         H     H     CF.sub.3                                                                              H    OCHMe.sub.2                            CH   Me         H     H     CF.sub.3                                                                              H    SMe                                    CH   Me         H     H     CF.sub.3                                                                              H    CHF.sub.2                              CH   Et         H     H     CF.sub.3                                                                              H    CHF.sub.2                              CH   Me         H     H     OCF.sub.3                                                                             H    CHF.sub.2                              CH   Me         H     H     CF.sub.3                                                                              H    OCF.sub.2 CHF.sub.2                    CH   Me         H     H     CF.sub.3                                                                              H    Cl                                     CH   MeCHCH     H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              H    CHCHCF.sub.3                           CH   Me         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             Et   H          H     CF.sub.3                                                                             H      OCHF.sub.2                                  CH   Et         H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me.sub.2 N H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   MeNH       H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     H     OMe    H    CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              H    SCHF.sub.2                             CH   Me         H     H     CF.sub.3                                                                              H    SO.sub.2 CHF.sub.2                     CH   MeO        H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   MeS        H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              Me   CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              CN   CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              OMe  CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              Cl   CF.sub.3                               N    Me         H     H     CF.sub.3                                                                              H    CF.sub.3                               N    Et         H     H     CF.sub.3                                                                              H    CF.sub.3                               N    Me         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             N    Et         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             N    Me         H     H     OCF.sub.3                                                                             H    CF.sub.3                               N    Me         H     H     OCHF.sub.2                                                                            H    CF.sub.3                               N    Me         H     H     CN     H    CF.sub.3                               N    Et         H     H     CN     H    CF.sub.3                               N    Me         H     H     OCF.sub.3                                                                             H    OCHF.sub.2                             N    Me         H     H     CF.sub.3                                                                              H    OMe                                    N    Me         H     H     SCF.sub.3                                                                             H    CF.sub.3                               ______________________________________                                    

                  TABLE IV                                                         ______________________________________                                          ##STR23##                     Id                                              X    R          R.sup.1                                                                              R.sup.2                                                                              R.sup.3                                                                               R.sup.4                                                                             R.sup.5                                ______________________________________                                         CH   Me         H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Et         H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   n-Pr       H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     H     OCF.sub.3                                                                             H    CF.sub.3                               CH   Et         H     H     OCF.sub.3                                                                             H    CF.sub.3                               CH   n-Pr       H     H     OCF.sub.3                                                                             H    CF.sub.3                               CH   Me         H     H     OCHF.sub.2                                                                            H    CF.sub.3                               CH   Me         H     H     OCF.sub.3                                                                             H    OCHF.sub.2                             CH   Me         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             CH   Me         F     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     6-F   CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     4-F   CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     2-OMe CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     2-CF.sub.3                                                                           H      H    CF.sub.3                               CH   Me         H     H     Cl     H    CF.sub.3                               CH   Me         H     H     Br     H    CF.sub.3                               CH   Et         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             CH   Me         H     H     CN     H    CF.sub.3                               CH   Et         H     H     CN     H    CF.sub.3                               CH   Me         H     H     SCF.sub.3                                                                             H    CF.sub.3                               CH   Me         H     H     H      H    CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              H    OCH.sub.2 CF.sub.3                     CH   Me         H     H     CF.sub.3                                                                              H    SCF.sub.3                              CH   Me         H     H     CF.sub.3                                                                              H    OMe                                    CH   Et         H     H     CF.sub.3                                                                              H    OEt                                    CH   Me         H     H     CF.sub.3                                                                              H    OCHMe.sub.2                            CH   Me         H     H     CF.sub.3                                                                              H    SMe                                    CH   Me         H     H     CF.sub.3                                                                              H    CHF.sub.2                              CH   Et         H     H     CF.sub.3                                                                              H    CHF.sub.2                              CH   Me         H     H     OCF.sub.3                                                                             H    CHF.sub.2                              CH   Me         H     H     CF.sub.3                                                                              H    OCF.sub.2 CHF.sub.2                    CH   Me         H     H     CF.sub.3                                                                              H    Cl                                     CH   MeCHCH     H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              H    CHCHCF.sub.3                           CH   Me         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             CH   Et         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             CH   MeOCH.sub.2                                                                               H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me.sub.2 N H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   MeNH       H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     H     OMe    H    CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              H    SCHF.sub.2                             CH   Me         H     H     CF.sub.3                                                                              H    SO.sub.2 CHF.sub.2                     CH   MeO        H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   MeS        H     H     CF.sub.3                                                                              H    CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              Me   CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              CN   CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              OMe  CF.sub.3                               CH   Me         H     H     CF.sub.3                                                                              Cl   CF.sub.3                               N    Me         H     H     CF.sub.3                                                                              H    CF.sub.3                               N    Et         H     H     CF.sub.3                                                                              H    CF.sub.3                               N    Me         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             N    Et         H     H     CF.sub.3                                                                              H    OCHF.sub.2                             N    Me         H     H     OCF.sub.3                                                                             H    CF.sub.3                               N    Me         H     H     OCHF.sub.2                                                                            H    CF.sub.3                               N    Me         H     H     CN     H    CF.sub.3                               N    Et         H     H     CN     H    CF.sub.3                               N    Me         H     H     OCF.sub.3                                                                             H    OCHF.sub.2                             N    Me         H     H     CF.sub.3                                                                              H    OMe                                    N    Me         H     H     SCF.sub.3                                                                             H    CF.sub.3                               ______________________________________                                    

                  TABLE V                                                          ______________________________________                                          ##STR24##                     Ie                                              X    R           R.sup.1                                                                              R.sup.2                                                                               R.sup.3                                                                               R.sup.5                                   ______________________________________                                         CH   Me          H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Et          H     H      CF.sub.3                                                                              CF.sub.3                                  CH   n-Pr        H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     H      OCF.sub.3                                                                             CF.sub.3                                  CH   Et          H     H      OCF.sub.3                                                                             CF.sub.3                                  CH   n-Pr        H     H      OCF.sub.3                                                                             CF.sub.3                                  CH   Me          H     H      OCHF.sub.2                                                                            CF.sub.3                                  CH   Me          H     H      OCF.sub.3                                                                             OCHF.sub.2                                CH   Me          H     H      CF.sub.3                                                                              OCHF.sub.2                                CH   Me          F     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     6-F    CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     4-F    CF.sub.3                                                                              CF.sub. 3                                 CH   Me          H     2-OMe  CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     2-CF.sub.3                                                                            H      CF.sub.3                                  CH   Me          H     H      Cl     CF.sub.3                                  CH   Et          H     H      CF.sub.3                                                                              OCHF.sub.2                                CH   Me          H     H      Br     CF.sub.3                                  CH   Me          H     H      CN     CF.sub.3                                  CH   Et          H     H      CN     CF.sub.3                                  CH   Me          H     H      SCF.sub.3                                                                             CF.sub.3                                  CH   Me          H     H      H      CF.sub.3                                  CH   Me          H     H      CF.sub.3                                                                              OCH.sub.2 CF.sub.3                        CH   Me          H     H      CF.sub.3                                                                              SCF.sub.3                                 CH   Me          H     H      CF.sub.3                                                                              OMe                                       CH   Et          H     H      CF.sub.3                                                                              OEt                                       CH   Me          H     H      CF.sub.3                                                                              OCHMe.sub.2                               CH   Me          H     H      CF.sub.3                                                                              SMe                                       CH   Me          H     H      CF.sub.3                                                                              CHF.sub.2                                 CH   Et          H     H      CF.sub.3                                                                              CHF.sub.2                                 CH   Me          H     H      OCF.sub.3                                                                             CHF.sub.2                                 CH   Me          H     H      CF.sub.3                                                                              OCF.sub.2 CHF.sub.2                       CH   Me          H     H      CF.sub.3                                                                              Cl                                        CH   MeCHCH      H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     H      CF.sub.3                                                                              CHCHCF.sub.3                              CH   Me          H     H      CF.sub.3                                                                              OCHF.sub.2                                CH   Et          H     H      CF.sub.3                                                                              OCHF.sub.2                                CH   MeOCH.sub.2 H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me.sub.2 N  H     H      CF.sub.3                                                                              CF.sub.3                                  CH   MeNH        H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     H      OMe    CF.sub.3                                  CH   Me          H     H      CF.sub.3                                                                              SCHF.sub.2                                CH   Me          H     H      CF.sub.3                                                                              SO.sub.2 CHF.sub.2                        CH   MeO         H     H      CF.sub.3                                                                              CF.sub.3                                  CH   MeS         H     H      CF.sub.3                                                                              CF.sub.3                                  N    Me          H     H      CF.sub.3                                                                              CF.sub.3                                  N    Et          H     H      CF.sub.3                                                                              CF.sub.3                                  N    Me          H     H      CF.sub.3                                                                              OCHF.sub.2                                N    Et          H     H      CF.sub.3                                                                              OCHF.sub.2                                N    Me          H     H      OCF.sub.3                                                                             CF.sub.3                                  N    Me          H     H      OCHF.sub.2                                                                            CF.sub.3                                  N    Me          H     H      CN     CF.sub.3                                  N    Et          H     H      CN     CF.sub.3                                  N    Me          H     H      OCF.sub.3                                                                             OCHF.sub.2                                N    Me          H     H      CF.sub.3                                                                              OMe                                       N    Me          H     H      SCF.sub.3                                                                             CF.sub.3                                  ______________________________________                                    

                  TABLE VI                                                         ______________________________________                                          ##STR25##                     If                                              X    R           R.sup.1                                                                              R.sup.2                                                                               R.sup.3                                                                               R.sup.5                                   ______________________________________                                         CH   Me          H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Et          H     H      CF.sub.3                                                                              CF.sub.3                                  CH   n-Pr        H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     H      OCF.sub.3                                                                             CF.sub.3                                  CH   Et          H     H      OCF.sub.3                                                                             CF.sub.3                                  CH   n-Pr        H     H      OCF.sub.3                                                                             CF.sub.3                                  CH   Me          H     H      OCHF.sub.2                                                                            CF.sub.3                                  CH   Me          H     H      OCF.sub.3                                                                             OCHF.sub.2                                CH   Me          H     H      CF.sub.3                                                                              OCHF.sub.2                                CH   Me          F     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     6-F    CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     4-F    CF.sub.3                                                                              CF.sub. 3                                 CH   Me          H     2-OMe  CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     2-CF.sub.3                                                                            H      CF.sub.3                                  CH   Me          H     H      Cl     CF.sub.3                                  CH   Et          H     H      CF.sub.3                                                                              OCHF.sub.2                                CH   Me          H     H      Br     CF.sub.3                                  CH   Me          H     H      CN     CF.sub.3                                  CH   Et          H     H      CN     CF.sub.3                                  CH   Me          H     H      SCF.sub.3                                                                             CF.sub.3                                  CH   Me          H     H      H      CF.sub.3                                  CH   Me          H     H      CF.sub.3                                                                              OCH.sub.2 CF.sub.3                        CH   Me          H     H      CF.sub.3                                                                              SCF.sub.3                                 CH   Me          H     H      CF.sub.3                                                                              OMe                                       CH   Et          H     H      CF.sub.3                                                                              OEt                                       CH   Me          H     H      CF.sub.3                                                                              OCHMe.sub.2                               CH   Me          H     H      CF.sub.3                                                                              SMe                                       CH   Me          H     H      CF.sub.3                                                                              CHF.sub.2                                 CH   Et          H     H      CF.sub.3                                                                              CHF.sub.2                                 CH   Me          H     H      OCF.sub.3                                                                             CHF.sub.2                                 CH   Me          H     H      CF.sub.3                                                                              OCF.sub.2 CHF.sub.2                       CH   Me          H     H      CF.sub.3                                                                              Cl                                        CH   MeCHCH      H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     H      CF.sub.3                                                                              CHCHCF.sub.3                              CH   Me          H     H      CF.sub.3                                                                              OCHF.sub.2                                CH   Et          H     H      CF.sub.3                                                                              OCHF.sub.2                                CH   MeOCH.sub.2 H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me.sub.2 N  H     H      CF.sub.3                                                                              CF.sub.3                                  CH   MeNH        H     H      CF.sub.3                                                                              CF.sub.3                                  CH   Me          H     H      OMe    CF.sub.3                                  CH   Me          H     H      CF.sub.3                                                                              SCHF.sub.2                                CH   Me          H     H      CF.sub.3                                                                              SO.sub.2 CHF.sub.2                        CH   MeO         H     H      CF.sub.3                                                                              CF.sub.3                                  CH   MeS         H     H      CF.sub.3                                                                              CF.sub.3                                  N    Me          H     H      CF.sub.3                                                                              CF.sub.3                                  N    Et          H     H      CF.sub.3                                                                              CF.sub.3                                  N    Me          H     H      CF.sub.3                                                                              OCHF.sub.2                                N    Et          H     H      CF.sub.3                                                                              OCHF.sub.2                                N    Me          H     H      OCF.sub.3                                                                             CF.sub.3                                  N    Me          H     H      OCHF.sub.2                                                                            CF.sub.3                                  N    Me          H     H      CN     CF.sub.3                                  N    Et          H     H      CN     CF.sub.3                                  N    Me          H     H      OCF.sub.3                                                                             OCHF.sub.2                                N    Me          H     H      CF.sub.3                                                                              OMe                                       N    Me          H     H      SCF.sub.3                                                                             CF.sub.3                                  ______________________________________                                    

                  TABLE VII                                                        ______________________________________                                          ##STR26##                     Ig                                              X    R          R.sup.1                                                                              R.sup.2                                                                              R.sup.3                                                                               R.sup.5  R.sup.8                            ______________________________________                                         CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Et         H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   n-Pr       H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     H     OCF.sub.3                                                                             CF.sub.3 H                                  CH   Et         H     H     OCF.sub.3                                                                             CF.sub.3 H                                  CH   n-Pr       H     H     OCF.sub.3                                                                             CF.sub.3 H                                  CH   Me         H     H     OCHF.sub.2                                                                            CF.sub.3 H                                  CH   Me         H     H     OCF.sub.3                                                                             OCHF.sub.2                                                                              H                                  CH   Me         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  CH   Me         F     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     6-F   CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     4-F   CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     2-OMe CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     2-CF.sub.3                                                                           H      CF.sub.3 H                                  CH   Me         H     H     Cl     CF.sub.3 H                                  CH   Et         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  CH   Me         H     H     Br     CF.sub.3 H                                  CH   Me         H     H     CN     CF.sub.3 H                                  CH   Et         H     H     CN     CF.sub.3 H                                  CH   Me         H     H     SCF.sub.3                                                                             CF.sub.3 H                                  CH   Me         H     H     H      CF.sub.3 H                                  CH   Me         H     H     CF.sub.3                                                                              OCH.sub.2 CF.sub.3                                                                      H                                  CH   Me         H     H     CF.sub.3                                                                              SCF.sub.3                                                                               H                                  CH   Me         H     H     CF.sub.3                                                                              OMe      H                                  CH   Et         H     H     CF.sub.3                                                                              OEt      H                                  CH   Me         H     H     CF.sub.3                                                                              OCHMe.sub.2                                                                             H                                  CH   Me         H     H     CF.sub.3                                                                              SMe      H                                  CH   Me         H     H     CF.sub.3                                                                              CHF.sub.2                                                                               H                                  CH   Et         H     H     CF.sub.3                                                                              CHF.sub.2                                                                               H                                  CH   Me         H     H     OCF.sub.3                                                                             CHF.sub.2                                                                               H                                  CH   Me         H     H     CF.sub.3                                                                              OCF.sub.2 CHF.sub.2                                                                     H                                  CH   Me         H     H     CF.sub.3                                                                              Cl       H                                  CH   MeCHCH     H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     H     CF.sub.3                                                                              CHCHCF.sub.3                                                                            H                                  CH   Me         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  CH   Et         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  CH   MeOCH.sub.2                                                                               H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me.sub.2 N H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   MeNH       H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     H     OMe    CF.sub.3 H                                  CH   Me         H     H     CF.sub.3                                                                              SCHF.sub.2                                                                              H                                  CH   Me         H     H     CF.sub.3                                                                              SO.sub.2 CHF.sub.2                                                                      H                                  CH   MeO        H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   MeS        H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 Me                                 CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 CN                                 CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 OMe                                CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 Cl                                 N    Me         H     H     CF.sub.3                                                                              CF.sub.3 H                                  N    Et         H     H     CF.sub.3                                                                              CF.sub.3 H                                  N    Me         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  N    Et         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  N    Me         H     H     OCF.sub.3                                                                             CF.sub.3 H                                  N    Me         H     H     OCHF.sub.2                                                                            CF.sub.3 H                                  N    Me         H     H     CN     CF.sub. 3                                                                               H                                  N    Et         H     H     CN     CF.sub.3 H                                  N    Me         H     H     OCF.sub.3                                                                             OCHF.sub.2                                                                              H                                  N    Me         H     H     CF.sub.3                                                                              OMe      H                                  N    Me         H     H     SCF.sub.3                                                                             CF.sub.3 H                                  ______________________________________                                    

                  TABLE VIII                                                       ______________________________________                                          ##STR27##                     Ih                                              X    R          R.sup.1                                                                              R.sup.2                                                                              R.sup.3                                                                               R.sup.5  R.sup.8                            ______________________________________                                         CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Et         H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   n-Pr       H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     H     OCF.sub.3                                                                             CF.sub.3 H                                  CH   Et         H     H     OCF.sub.3                                                                             CF.sub.3 H                                  CH   n-Pr       H     H     OCF.sub.3                                                                             CF.sub.3 H                                  CH   Me         H     H     OCHF.sub.2                                                                            CF.sub.3 H                                  CH   Me         H     H     OCF.sub.3                                                                             OCHF.sub.2                                                                              H                                  CH   Me         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  CH   Me         F     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     6-F   CF.sub.3                                                                              CF.sub. 3                                                                               H                                  CH   Me         H     4-F   CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     2-OMe CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     2-CF.sub.3                                                                           H      CF.sub.3 h                                  CH   Me         H     H     Cl     CF.sub.3 H                                  CH   Et         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  CH   Me         H     H     Br     CF.sub.3 H                                  CH   Me         H     H     CN     CF.sub.3 H                                  CH   Et         H     H     CN     CF.sub.3 H                                  CH   Me         H     H     SCF.sub.3                                                                             CF.sub.3 H                                  CH   Me         H     H     H      CF.sub.3 H                                  CH   Me         H     H     CF.sub.3                                                                              OCH.sub.2 CF.sub.3                                                                      H                                  CH   Me         H     H     CF.sub.3                                                                              SCF.sub.3                                                                               H                                  CH   Me         H     H     CF.sub.3                                                                              OMe      H                                  CH   Et         H     H     CF.sub.3                                                                              OEt      H                                  CH   Me         H     H     CF.sub.3                                                                              OCHMe.sub.2                                                                             H                                  CH   Me         H     H     CF.sub.3                                                                              SMe      H                                  CH   Me         H     H     CF.sub.3                                                                              CHF.sub.2                                                                               H                                  CH   Et         H     H     CF.sub.3                                                                              CHF.sub.2                                                                               H                                  CH   Me         H     H     OCF.sub.3                                                                             CHF.sub.2                                                                               H                                  CH   Me         H     H     CF.sub.3                                                                              OCF.sub.2 CHF.sub.2                                                                     H                                  CH   Me         H     H     CF.sub.3                                                                              Cl       H                                  CH   MeCHCH     H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     H     CF.sub.3                                                                              CHCHCF.sub.3                                                                            H                                  CH   Me         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  CH   Et         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  CH   MeOCH.sub.2                                                                               H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me.sub.2 N H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   MeNH       H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     H     OMe    CF.sub.3 H                                  CH   Me         H     H     CF.sub.3                                                                              SCHF.sub.2                                                                              H                                  CH   Me         H     H     CF.sub.3                                                                              SO.sub.2 CHF.sub.2                                                                      H                                  CH   MeO        H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   MeS        H     H     CF.sub.3                                                                              CF.sub.3 H                                  CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 Me                                 CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 CN                                 CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 OMe                                CH   Me         H     H     CF.sub.3                                                                              CF.sub.3 Cl                                 N    Me         H     H     CF.sub.3                                                                              CF.sub.3 H                                  N    Et         H     H     CF.sub.3                                                                              CF.sub.3 H                                  N    Me         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  N    Et         H     H     CF.sub.3                                                                              OCHF.sub.2                                                                              H                                  N    Me         H     H     OCF.sub.3                                                                             CF.sub.3 H                                  N    Me         H     H     OCHF.sub.2                                                                            CF.sub.3 H                                  N    Me         H     H     CN     CF.sub.3 H                                  N    Et         H     H     CN     CF.sub.3 H                                  N    Me         H     H     OCF.sub.3                                                                             OCHF.sub.2                                                                              H                                  N    Me         H     H     CF.sub.3                                                                              OMe      H                                  N    Me         H     H     SCF.sub.3                                                                             CF.sub.3 H                                  ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

    ______________________________________                                                     Active  Weight Percent*                                                        Ingredient                                                                             Diluent(s)                                                                               Surfactant(s)                                    ______________________________________                                         Wettable Powders                                                                             20-90      0-74     1-10                                         Oil Suspensions,                                                                              3-50     40-95     0-15                                         Emulsions, Solutions,                                                          (including Emulsifiable                                                        Concentrates)                                                                  Aqueous Suspension                                                                           10-50     40-84     1-20                                         Dusts          1-25     70-99     0-5                                          Granules and Pellets                                                                         0.1-95      5-99.9  0-15                                         High Strength 90-99      0-10     0-2                                          Compositions                                                                   ______________________________________                                          *Active ingredient plus at least one of a Surfactant or a Diluent equals       100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, N.Y., 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., N.Y., 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, Jun. 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

EXAMPLE A

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                     80%                                                   methyl)-phenyl]quinoxaline                                                     sodium alkylnaphthalenesulfonate                                                                        2%                                                    sodium ligninsulfonate   2%                                                    synthetic amorphous silica                                                                              3%                                                    kaolinite                13%                                                   ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.

EXAMPLE B

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                     50%                                                   methyl)-phenyl]quinoxaline                                                     sodium alkylnaphthalenesulfonate                                                                        2%                                                    low viscosity methyl cellulose                                                                          2%                                                    diatomaceous earth       46%                                                   ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.

EXAMPLE C

    ______________________________________                                         Granule                                                                        ______________________________________                                         Wettable Powder of Example B                                                                           5%                                                     attapulgite granules   95%                                                     (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                              ______________________________________                                    

A slurry of wettable powder containing solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

EXAMPLE D

    ______________________________________                                         Extruded Pellet                                                                ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                     25%                                                   methyl)-phenyl]quinoxaline                                                     anhydrous sodium sulfate 10%                                                   crude calcium ligninsulfonate                                                                            5%                                                   sodium alkylnaphthalenesulfonate                                                                         1%                                                   calcium/magnesium bentonite                                                                             59%                                                   ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

EXAMPLE E

    ______________________________________                                         Low Strength Granule                                                           ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                     1%                                                    methyl)-phenyl]quinoxaline                                                     N,N-dimethylformamide    9%                                                    attapulgite granules     90%                                                   (U.S.S. 20 to 40 sieve)                                                        ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.

EXAMPLE F

    ______________________________________                                         Granule                                                                        ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                     80%                                                   methyl)-phenyl]quinoxaline                                                     wetting agent             1%                                                   crude ligninsulfonate salt (containing                                                                  10%                                                   5-20 of the natural sugars)                                                    attapulgite clay          9%                                                   ______________________________________                                    

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

EXAMPLE G

    ______________________________________                                         Aqueous Suspension                                                             ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                      40%                                                  methyl)-phenyl]quinoxaline                                                     polyacrylic acid thickener                                                                              0.3%                                                  dodecylphenol polyethylene glycol ether                                                                 0.5%                                                  disodium phosphate         1%                                                  monosodium phosphate     0.5%                                                  polyvinyl alcohol        1.0%                                                  water                    56.7%                                                 ______________________________________                                    

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

EXAMPLE H

    ______________________________________                                         High Strength Concentrate                                                      ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                      99%                                                  methyl)-phenyl]quinoxaline                                                     silica aerogel           0.5%                                                  synthetic amorphous silica                                                                              0.5%                                                  ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

EXAMPLE I

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                      90%                                                  methyl)-phenyl]quinoxaline                                                     dioctyl sodium sulfosuccinate                                                                           0.1%                                                  synthetic fine silica    9.9%                                                  ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.

EXAMPLE J

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                     40%                                                   methyl)-phenyl]quinoxaline                                                     sodium ligninsulfonate   20%                                                   montmorillonite clay     40%                                                   ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.

EXAMPLE K

    ______________________________________                                         Oil Suspension                                                                 ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                     35%                                                   methyl)-phenyl]quinoxaline                                                     blend of polyalcohol carboxylic                                                                          6%                                                   esters and oil soluble petroleum                                               sulfonates                                                                     xylene                   59%                                                   ______________________________________                                    

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

EXAMPLE L

    ______________________________________                                         Dust                                                                           ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                     10%                                                   methyl)-phenyl]quinoxaline                                                     attapulgite              10%                                                   Pyrophyllite             80%                                                   ______________________________________                                    

The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

EXAMPLE M

    ______________________________________                                         Oil Suspension                                                                 ______________________________________                                         α-(difluoromethoxy)-6-methyl-8-[3-(trifluoro-                                                     25%                                                   methyl)-phenyl]quinoxaline                                                     polyoxyethylene sorbitol hexaoleate                                                                      5%                                                   highly aliphatic hydrocarbon oil                                                                        70%                                                   ______________________________________                                    

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

UTILITY

Test results indicate compounds of this invention are active postemergence and preemergence herbicides. Many compounds in this invention are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops such as barley (Hordeum vulgare), corn (Zea mays), cotton (Gossypium hirsutum), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max) and wheat (Triticum aestivum). Grass and broadleaf weed species controlled include, but are not limited to, barnyardgrass (Echinochloa crusgalli), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), cheatgrass (Bromus secalinus), chickweed (Stellaria media), crabgrass (Digitaria spp.), foxtail (Setaria spp.), lambsquarters (Chenopodium spp.), velvetleaf (Afutilon theophrasti), wild buckwheat (Polygonum convolvulus) and wild oats (Avena fatua).

These compounds also have utility for weed control of selected vegetation in specified areas such as around storage tanks, parking lots, highways, and railways; in fallow crop areas; and in citrus and plantation crops such as banana, coffee, oil palm, and rubber.

Rates of application for compounds of this invention are determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general terms, the subject compounds should be applied at rates from 0.01 to 20 kg/ha with a preferred rate range of 0.02 to 2 kg/ha. Although a small number of compounds show slight herbicidal activity at the rates tested, it is anticipated these compounds are herbicidally active at higher application rates. One skilled in the art can easily determine application rates necessary for desired level of weed control.

Compounds of this invention may be used alone or in combination with other commercial herbicides, insecticides, or fungicides. The following list exemplifies some of the herbicides suitable for use in mixtures. A combination of a compound from this invention with one or more of the following herbicides may be particularly useful for weed control.

    ______________________________________                                         Common Name   Chemical Name                                                    ______________________________________                                         acetochlor    2-chloro-N-(ethoxymethyl)-N-                                                   (2-ethyl-6-methylphenyl)-                                                      acetamide                                                        acifluorfen   5-[2-chloro-4-(trifluoromethyl)-                                               phenoxy]-2-nitrobenzoic acid                                     aclonifen     2-chloro-6-nitro-3-phenoxybenzen-                                              amine                                                            acrolein      2-propenal                                                       alachlor      2-chloro-N-(2,6-diethylphenyl)-N-                                              (methoxymethyl)acetamide                                         alloxydim     methyl 2,2-dimethyl-4,6-dioxo-                                                 5-[1-[(2-propenyloxy)amino]-                                                   butylidene]cyclohexanecar-                                                     boxylate                                                         ametryn       N-ethyl-N'-(1-methylethyl)-6-                                                  (methylthio)-1,3,5-triazine-2,4-                                               diamine                                                          amitrole      1H-1,2,4-triazol-3-amine                                         AMS           ammonium sulfamate                                               anilofos      S-[2-[(4-chlorophenyl)(1-methyl-                                               ethyl)amino]-2-oxoethyl]                                                       O,O-dimethylphosphorodithioate                                   asulam        methyl [(4-aminophenyl)sulfonyl]-                                              carbamate                                                        atrazine      6-chloro-N-ethyl-N'-(1-methyl-                                                 ethyl)-1,3,5-triazine-2,4-                                                     diamine                                                          aziprotryne   4-azido-N-(1-methylethyl)-6-                                                   methylthio-1,3,5-triazin-2-amine                                 azoluron      N-(1-ethyl-1H-pyrazol-5-yl)-N'-                                                phenylurea                                                       barban        4-chloro-2-butynyl 3-chloro-                                                   carbamate                                                        benazolin     4-chloro-2-oxo-3(2H)-benzothiazole                                             acetic acid                                                      benfluralin   N-butyl-N-ethyl-2,6-dinitro-4-                                                 (trifluoromethyl)benzenamine                                     bensulfuron   2-[[[[[(4,6-dimethoxy-2-pyrimi-                                                dinyl)amino]methylcarbonyl]-                                                   amino]sulfonyl]methyl]benzoic                                                  acid, methyl ester                                               bensulide     O,O-bis(1-methylethyl) S-[2-                                                   [(phenylsulfonyl)amino]ethyl]-                                                 phosphorodithioate                                               bentazon      3-(1-methylethyl)-(1H)-2,1,3-                                                  benzothiadiazin-4(3H)-one,                                                     2,2-dioxide                                                      benzofluor    N-[4-(ethylthio)-2-(trifluoro-                                                 methyl)phenyl]methanesulfonamide                                 benzoylprop   N-benzoyl-N-(3,4-dichlorophenyl)-                                              DL-alanine                                                       benzthiazuron N-2-benzothiazolyl-N'-methylurea                                 bialaphos     4-(hydroxymethylphosphinyl)-L-2-                                               aminobutanoyl-L-alanyl-L-alanine                                 bifenox       methyl 5-(2,4-dichlorophenoxy)-2-                                              nitrobenzoate                                                    bromacil      5-bromo-6-methyl-3-(1-methyl-                                                  propyl)-2,4(1H,3H)pyrimidine-                                                  dione                                                            *bromobutide  (+)2-bromo-3,3-dimethyl-N-(1-                                                  methyl-1-phenylethyl)butanamide                                  bromofenoxim  3,5-dibromo-4-hydroxybenzaldhyde                                               O-(2,4-dinitrophenyl)oxime                                       bromoxynil    3,5-dibromo-4-hydroxybenzonitrile                                bromuron      N'-(4-bromophenyl)-N,N-dimethyl-                                               urea                                                             buminafos     dibutyl [1-(butylamino)cyclo-                                                  hexyl]phosphonate                                                butachlor     N-(butoxymethyl)-2-chloro-N-(2,6-                                              diethylphenyl)acetamide                                          butamifos     O-ethyl O-(5-methyl-2-nitro-                                                   phenyl)(1methylpropyl)phosphor-                                                amidothioate                                                     buthidazole   3-[5-(1,1-dimethylethyl)-1,3,4-                                                thiadiazol-2-yl]-4-hydroxy-1-                                                  methyl-2-imidazolidinone                                         butralin      4-(1,1-dimethylethyl)-N-(1-methyl-                                             propyl)-2,6-dinitrobenzenamine                                   butylate      S-ethyl bis(2-methylpropyl)-                                                   carbamothioate                                                   cacodylic     dimethyl arsinic oxide                                           acid                                                                           carbetamide   (R)-N-ethyl-2-[[(phenylamino)-                                                 carbonyl]oxy]propanamide                                         CDAA          2-chloro-N,N-di-2-propenylacet-                                                amide                                                            CDEC          2-chloroallyl diethyldithio-                                                   carbamate                                                        chlomethoxyfen                                                                               4-(2,4-dichlorophenoxy)-2-methoxy-                                             1-nitrobenzene                                                   chloramben    3-amino-2,5-dichlorobenzoic acid                                 chlorbromuron 3-(4-bromo-3-chlorophenyl)-1-                                                  methoxy-1-methylurea                                             chlorbufam    1-methyl-2-propynl(3-chloro-                                                   phenyl)carbamate                                                 chlorfenac    2,3,6-trichlorobenzeneacetic acid                                chlorflurecol-                                                                               methyl 2-chloro-9-hydroxy-9H-                                    methyl        fluorene-9-carboxylate                                           chloridazon   5-amino-4-chloro-2-phenyl-3(2H)-                                               pyridazinone                                                     chlorimuron   2-[[[[(4-chloro-6-methoxy-2-                                                   pyrimidinyl)ethylamino]-                                                       carbonyl]amino]sulfonyl]-                                                      benzoic acid, ethyl ester                                        chlornitrofen 1,3,5-trichloro-2-(4-nitro-                                                    phenoxy)benzene                                                  chloropicrin  trichloronitromethane                                            chloroxuron   N'-[4-(4-chlorophenoxy)phenyl]-                                                N,N-dimethylurea                                                 chlorpropham  1-methylethyl 3-chloro-                                                        phenylcarbamate                                                  chlorsulfuron 2-chloro-N-[[(4-methoxy-6-                                                     methyl-1,3,5-triazin-2-yl)-                                                    amino] carbonyl]  benzene-                                                     sulfonamide                                                      chlorthal-    dimethyl 2,3,5,6-tetrachloro-                                    dimethyl      1,4-benzenedicarboxylate                                         chlorthiamid  2,6-dichlorobenzene carbothioamide                               chlortoluron  N'-(3-chloro-4-methylphenyl)-N,N-                                              dimethylurea                                                     cinmethylin   exo-1-methyl-4-(1-methylethyl)-                                                2-[(2-methylphenyl)methoxy]-7-                                                 oxabicyclo[2.2.1]heptane                                         clethodim     (E,E)-(+)-2-[1-[[(3-chloro-2-                                                  propenyl)oxy]imino]propyl]-                                                    5-[2-(ethylthio)propyl]-3-                                                     hydroxy-2-cyclohexen-1-one                                       clomazone     2-[(2-chlorophenyl)methyl]-                                                    4,4-dimethyl-3-isoxazolidinone                                   cloproxydim   (E,E)-2-[1-[[(3-chloro-2-                                                      propenyl)oxy)imino]butyl]-5-                                                   [2-(ethylthio)propyl]-                                                         3-hydroxy-2-cyclohexen-1-one                                     clopyralid    3,6-dichloro-2-pyridinecarboxylic                                              acid                                                             CMA           calcium salt of MAA                                              cyanazine     2-[[4-chloro-6-(ethylamino)-                                                   1,3,5-triazin-2-yl]amino]-2-                                                   methylpropanenitrile                                             cycloate      S-ethyl cyclohexylethyl-                                                       carbamothioate                                                   cycloxydim    2-[1-ethoxyimino)butyl]-3-hydroxy-                                             5-(tetrahydro-2H-thio-                                                         pyran-3-yl)-2-cyclohexene-                                                     1-one                                                            cycluron      3-cyclooctyl-1,1-dimethylurea                                    cyperquat     1-methyl-4-phenylpyridinium                                      cyprazine     2-chloro-4-(cyclopropylamino)-                                                 6-(isopropylamino)-s-triazine                                    cyprazole     N-[5-(2-chloro-1,1-dimethylethyl)-                                             1,3,4-thiadiazol-2-yl]cyclo-                                                   propanecarboxamide                                               cypromid      3',4'-dichlorocyclopropanecar-                                                 boxanilide                                                       dalapon       2,2-dichloropropanoic acid                                       dazomet       tetrahydro-3,5-dimethyl-2H-1,3,5-                                              thiadiazine-2-thione                                             DCPA          dimethyl 2,3,5,6-tetrachloro-1,4-                                              benzenedicarboxylate                                             desmedipham   ethyl [3-[[(phenylamino)carbonyl]-                                             oxy]phenyl]carbamate                                             desmetryn     2-(isopropylamino)-4-(methyl-                                                  amino)-6-(methylthio)-s-triazine                                 diallate      S-(2,3-dichloro-2-propenyl)bis(1-                                              methylethyl)carbamothioate                                       dicamba       3,6-dichloro-2-methoxybenzoic acid                               dichlobenil   2,6-dichlorobenzonitrile                                         dichlorprop   (+)-2-(2,4-dichlorophenoxy)pro-                                                panoic acid                                                      *diclofop-    (+)-2-[4-(2,4-dichlorophenoxy)-                                  methyl        phenoxy]propanoic acid, methyl                                                 ester                                                            diethatyl     N-(chloroacetyl)-N-(2,6-diethyl-                                               phenyl)glycine                                                   difenoxuron   N'-[4-(4-methoxyphenoxy)phenyl]-                                               N,N-dimethylurea                                                 difenzoquat   1,2-dimethyl-3,5-diphenyl-1H-                                                  pyrazolium ion                                                   diflufenican  N-(2,4-difluorophenyl)-2-(3-tri-                                               fluoromethylphenoxy)pyridine-                                                  3-carboxamide                                                    dimefuron     N'-[3-chloro-4-[5-(1,1-dimethyl-                                               ethyl)-2-oxo-1,3,4-oxadiazol-                                                  3(2H)-yl]phenyl]-N,N-dimethyl-                                                 urea                                                             dimethachlor  2-chloro-N-(2,6-dimethylphenyl)-                                               N-(2-methoxyethyl)acetamide                                      dimethametryn N-(1,2-dimethylpropyl)-N'-ethyl-6-                                             (methylthio)-1,3,5-triazine-2,4-                                               diamine                                                          dimethipin    2,3-dihydro-5,6-dimethyl-1,4-                                                  dithiin 1,1,4,4-tetraoxide                                       dimethylarsinic                                                                              dimethylarsinic acid                                             dinitramine   N3,N3-diethyl-2,4-dinitro-6-                                                   (trifluoromethyl)-1,3-benzene-                                                 diamine                                                          dinoseb       2-(1-methylpropyl-4,6-dinitro-                                                 phenol                                                           dinoterb      2-(1,1-dimethylethyl)-4,6-dinitro-                                             phenol                                                           diphenamid    N,N-dimethyl-a-phenylbenzene-                                                  acetamide                                                        dipropetryn   6-(ethylthio)-N,N'-bis(1-methyl-                                               ethyl)-1,3,5-triazine-2,4-                                                     diamine                                                          diquat        6,7-dihydrodipyrido[1,2-a:2',-                                                 1'-c]pyrazinediium ion                                           diuron        N'-(3,4-dichlorophenyl)-N,N-                                                   dimethylurea                                                     DNOC          2-methyl-4,6-dinitrophenol                                       DPX-V9360     2-[[(4,6-dimethoxypyrimidin-                                                   2-yl)aminocarbonyl]amino-                                                      sulfonyl]-N,N-dimethyl-                                                        3-pyridinecarboxamide                                            DSMA          disodium salt of MAA                                             dymron        N-(4-methylphenyl)-N'-(1-methyl-                                               1-phenylethyl)urea                                               eglinazine-ethyl                                                                             N-[4-chloro-6-(ethylamino)-                                                    1,3,5-triazin-2-yl]glycine                                                     ethyl ester                                                      endothall     7-oxabicyclo[2.2.1]heptane-                                                    2,3-dicarboxylic acid                                            EPTC          S-ethyl dipropylcarbamothioate                                   ethalfluralin N-ethyl-N-(2-methyl-2-propenyl)-                                               2,6-dinitro-4-(trifluoromethyl)-                                               benzenamine                                                      ethidimuron   N-[5-(ethylsulfonyl)-1,3,4-thia-                                               diazol-2-yl]-N,N'-dimethylurea                                   *ethofumesate (+)-2-ethoxy-2,3-dihydro-3,3-                                                  dimethyl-5-benzofuranyl                                                        methanesulfonate                                                 fenac         2,3,6-trichlorobenzeneacetic acid                                *fenoprop     (+)-2-(2,4,5-trichlorophenoxy)-                                                propanoic acid                                                   *fenoxaprop   (+)-2-[4-[(6-chloro-2-benzoxa-                                                 zolyl)oxy]phenoxy]propanoic acid                                 fenuron       N,N-dimethyl-N'-phenylurea                                       fenuron TCA   Salt of fenuron and TCA                                          flamprop-M-   1-methylethyl N-benzoyl-N-                                       isopropyl     (3-chloro-4-fluorophenyl)-                                                     D-alanine                                                        flamprop-methyl                                                                              methyl N-benzoyl-N-(3-chloro-4-                                                fluorophenyl)-DL-alaninate                                       *fluazifop    (+)-2-[4-[[5-(trifluoromethyl)-                                                2-pyridinyl]oxy]phenoxy]-                                                      propanoic acid                                                   fluazifop-P   (R)-2-[4-[[5-(trifluoromethyl)-                                                2-pyridinyl]oxy]phenoxy]pro-                                                   panoic acid                                                      fluchloralin  N-(2-chloroethyl)-2,6-dinitro-                                                 N-propyl-4-(trifluoromethyl)-                                                  benzenamine                                                      fluometuron   N,N-dimethyl-N'-[3-(trifluoro-                                                 methyl)phenyl]urea                                               fluralin      N-butyl-N-ethyl-2,6-dinitro-4-                                                 (trifluoromethyl)benzenamine                                     fluorodifen   p-nitrophenyl a,a,a-trifluoro-                                                 2-nitro-p-tolyl ether                                            fluorogly-    carboxymethyl 5-[2-chloro-4-(tri-                                cofen         fluoromethyl)phenoxy]-                                                         2-nitrobenzoate                                                  flurecol-butyl                                                                               butyl 9-hydroxy-9H-fluorene-                                                   9-carboxylate                                                    fluridone     1-methyl-3-phenyl-5-[3-(trifluoro-                                             methyl)phenyl]-4(1H)-pyridinone                                  flurochloridone                                                                              3-chloro-4-(chloromethyl)-1-                                                   [3-(trifluoromethyl)phenyl]-                                                   2-pyrrolidinone                                                  fluroxypyr    [(4-amino-3,5-dichloro-6-fluoro-2-                                             pyridinyl)oxy]acetic acid                                        fomesafen     5-[2-chloro-4-(trifluoromethyl)-                                               phenoxy]-N-(methylsulfonyl)-                                                   2-nitrobenzamide                                                 fosamine-     ethyl hydrogen (aminocarbonyl)-                                  ammonium      phosphonate ammonium ethyl                                       glufosinate-  ammonium 2-amino-4-(hydroxymethyl-                               ammonium      phosphinyl)butanoate                                             glyphosate    N-(phosphonomethyl)glycine                                       haloxyfop     2-[4-[[3-chloro-5-(trifluoro-                                                  methyl)-2-pyridinyl]oxy]-                                                      phenoxy]propanoic acid                                           hexaflurate   potassium hexafluoroarsenate                                     hexazinone    3-cyclohexyl-6-(dimethylamino)-                                                1-methyl-1,3,5-triazine-                                                       2,4(1H,3H)dione                                                  imazametha-   6-(4-isopropyl-4-methyl-5-oxo-2-                                 benz          imidazolin-2-yl)-m-toluic acid,                                                methyl ester and 6-(4-isopropyl-                                               4-methyl-5-oxo-2-imidazolin-                                                   2-yl)-p-toluic acid, methyl                                                    ester                                                            imazapyr      (+)-2-[4,5-dihydro-4-methyl-4-                                                 (1-methylethyl)-5-oxo-1H-                                                      imidazol-2-yl]-3-pyridine-                                                     carboxylic acid                                                  imazaquin     2-[4,5-dihydro-4-methyl-4-(1-                                                  methylethyl)-5-oxo-1H-imidazol-                                                2-yl]-3-quinolinecarboxylic acid                                 imazethapyr   (+)-2-[4,5-dihydro-4-methyl-4-                                                 (1-methylethyl)-5-oxo-1H-                                                      imidazol-2-yl]-5-ethyl-3-                                                      pyridine carboxylic acid                                         ioxynil       4-hydroxy-3,5-diiodobenzonitrile                                 isocarbamid   N-(2-methylpropyl)-2-oxo-1-                                                    imidazolidinecarboxamide                                         isopropalin   4-(1-methylethyl)-2,6-dinitro-N,N-                                             dipropylbenzenamine                                              isoproturon   N-(4-isopropylphenyl)-N',N'-                                                   dimethylurea                                                     isouron       N'-[5-(1,1-dimethylethyl)-3-                                                   isoxazolyl]-N,N-dimethylurea                                     isoxaben      N-[3-(1-ethyl-1-methylpropyl)-5-                                               isoxazolyl]-2,6-dimethoxy-                                                     benzamide                                                        karbutilate   3-[[(dimethylamino)carbonyl]-                                                  amino]phenyl-(1,1-dimethyl-                                                    ethyl)carbamate                                                  lactofen      (+)-2-ethoxy-1-methyl-2-oxoethyl-                                              5-[2-chloro-4-(trifluoro-                                                      methyl)phenoxy]-2-nitrobenzoate                                  lenacil       3-cyclohexyl-6,7-dihydro-1H-                                                   cyclopentapyrimidine-2,4(3H,5H)-                                               dione                                                            linuron       N'-(3,4-dichlorophenyl)-N-methoxy-                                             N-methylurea                                                     MAA           methylarsonic acid                                               MAMA          monoammonium salt of MAA                                         MCPA          (4-chloro-2-methylphenoxy)acetic                                               acid                                                             MCPA-thioethyl                                                                               S-ethyl (4-chloro-2-methyl-                                                    phenoxy)ethanethioate                                            MCPB          4-(4-chloro-2-methylphenoxy)-                                                  butanoic acid                                                    mecoprop      (+)-2-(4-chloro-2-methylphenoxy)-                                              propanoic acid                                                   mefenacet     2-(2-benzothiazolyloxy)-N-methyl-                                              N-phenyl acetamide                                               mefluidide    N-[2,4-dimethyl-5-[[(trifluoro-                                                methyl)sulfonyl]amino]phenyl]-                                                 acetamide                                                        metamitron    4-amino-3-methyl-6-phenyl-1,2,4-                                               triazin-5(4H)-one                                                metazachlor   2-chloro-N-(2,6-dimethylphenyl)-N-                                             (1(H)-pyrazol-1-ylmethyl)-                                                     acetamide                                                        methabenz-    1,3-dimethyl-3-(2-benzothiazolyl)-                               thiazuron     urea                                                             methal-       N-(2-methyl-2-propenyl)-2,6-                                     propalin      dinitro-N-propyl-4-(trifluoro-                                                 methyl)benzenamide                                               metham        methylcarbamodithioic acid                                       methazole     2-(3,4-dichlorophenyl)-4-methyl-                                               1,2,4-oxadiazolidine-3,5-dione                                   methoxuron    N'-(3-chloro-4-methoxyphenyl)-N,N-                                             dimethylurea                                                     methoxyphenone                                                                               (4-methoxy-3-methylphenyl)(3-                                                  methylphenyl)methanone                                           methyldymron  N-methyl-N'-(1-methyl-1-phenyl-                                                ethyl)-N-phenylurea                                              metobromuron  N'-(4-bromophenyl)-N-methoxy-N-                                                methylurea                                                       metolachlor   2-chloro-N-(2-ethyl-6-methyl-                                                  phenyl)-N-(2-methoxy-1-methyl-                                                 ethyl)acetamide                                                  metoxuron     N'-(3-chloro-4-methoxyphenyl)-N,N-                                             dimethylurea                                                     metribuzin    4-amino-6-(1,1-dimethylethyl)-3-                                               (methylthio)-1,2,4-triazin-                                                    5(4H)-one                                                        metsulfuron   2-[[[[(4-methoxy-6-methyl-1,3,5-                                 methyl        triazin-2-yl)amino]carbonyl]-                                                  amino]sulfonyl]benzoic acid,                                                   methyl ester                                                     MH            1,2-dihydro-3,6-pyridazinedione                                  molinate      S-ethyl hexahydro-1H-azepine-                                                  1-carbothioate                                                   monalide      N-(4-chlorophenyl)-2,2-dimethyl-                                               pentanamide                                                      monolinuron   3-(p-chlorophenyl)-1-methoxy-                                                  1-methylurea                                                     monuron       N'-(4-chlorophenyl)-N,N-dimethyl-                                              urea                                                             MSMA          monosodium salt of MAA                                           naproanilide  2-(2-naphthalenyloxy)-N-phenyl-                                                propanamide                                                      napropamide   N,N-diethyl-2-(1-naphthalenyloxy)-                                             propanamide                                                      naptalam      2-[(1-naphthalenylamino)carbonyl]-                                             benzoic acid                                                     neburon       1-butyl-3-(3,4-dichlorophenyl)-                                                1-methylurea                                                     nitralin      4-methylsulfonyl-2,6-dinitro-N,N-                                              dipropylaniline                                                  nitrofen      2,4-dichloro-1-(4-nitrophenoxy)-                                               benzene                                                          nitrofluorfen 2-chloro-1-(4-nitrophenoxy)-4-                                                 (trifluoromethyl)benzene                                         norea         N,N-dimethyl-N'-(octahydro-4,7-                                                methano-1H-inden-5-yl)urea-                                                    3aa,4a,5a,7a,7aa-isomer                                          norflurazon   4-chloro-5-(methylamino)-2-[3-                                                 (trifluoromethyl)phenyl]-3(2H)-                                                pyridazinone                                                     orbencarb     S-[2-(chlorophenyl)methyl]diethyl-                                             carbamothioate                                                   oryzalin      4-(dipropylamino)-3,5-dinitro-                                                 benzenesulfonamide                                               oxadiazon     3-[2,4-dichloro-5-(1-methyl-                                                   ethoxy)phenyl]-5-(1,1-dimethyl-                                                ethyl)-1,3,4-oxadiazol-2(3H)-one                                 oxyfluorfen   2-chloro-1-(3-ethoxy-4-nitro-                                                  phenoxy)-4-(trifluoro-                                                         methyl)benzene                                                   paraquat      1,1'-dimethyl-4,4'-dipyridinium                                                ion                                                              pebulate      S-propyl butylethylcarbamothioate                                pendimethalin N-(1-ethylpropyl)-3,4-dimethyl-                                                2,6-dinitrobenzenamine                                           perfluidone   1,1,1-trifluoro-N-[2-methyl-4-                                                 (phenylsulfonyl)phenyl]methane-                                                sulfonamide                                                      phenisopham   3-[[(1-methylethoxy)carbonyl]-                                                 amino]phenyl ethylphenyl-                                                      carbamate                                                        phenmedipham  3-[(methoxycarbonyl)amino]phenyl                                               (3-methylphenyl)carbamate                                        picloram      4-amino-3,5,6-trichloro-2-                                                     pyridinecarboxylic acid                                          piperophos    S-[2-(2-methyl-1-piperidinyl)-                                                 2-oxo-ethyl]O,O-dipropyl                                                       phosphorodithioate                                               pretilachlor  2-chloro-N-(2,6-diethylphenyl)-                                                N-(2-propoxyethyl)acetamide                                      procyazine    2-[[4-chloro-6-(cyclopropylamino)-                                             1,3,5-triazine-2-yl]amino]-                                                    2-methylpropanenitrile                                           prodiamine    2,4-dinitro-N3,N3-dipropyl-6-                                                  (trifluoromethyl)-1,3-benzene-                                                 diamine                                                          profluralin   N-(cyclopropylmethyl)-2,6-dinitro-                                             N-propyl-4-(trifluoromethyl)-                                                  benzenamine                                                      proglinazine- N-[4-chloro-6-[(1-methylethyl)-                                  ethyl         amino]-1,3,5-triazin-2-yl]-                                                    glycine ethyl ester                                              prometon      6-methoxy-N,N'-bis(1-methylethyl)-                                             1,3,5-triazine-2,4-diamine                                       prometryn     N,N'-bis(1-methylethyl)-6-(methyl-                                             thio)-1,3,5-triazine-2,4-diamine                                 pronamide     3,5-dichloro-N-(1,1-dimethyl-2-                                                propynyl)benzamide                                               propachlor    2-chloro-N-(1-methylethyl)-N-                                                  phenylacetamide                                                  propanil      N-(3,4-dichlorophenyl)propanamide                                propaquizafop 2-[[(1-methylethylidene)amino]-                                                oxy]ethyl-2-[ 4-[(6-chloro-2-                                                  quinoxalinyl)oxy]phenoxy]-                                                     propanoate                                                       propazine     6-chloro-N,N'-bis(1-methylethyl)-                                              1,3,5-triazine-2,4-diamine                                       propham       1-methylethyl phenylcarbamate                                    propyzamide   3,5-dichloro-N-(1,1-dimethyl-2-                                                propynl)benzamide                                                prosulfalin   N-[[4-(dipropylamino)-3,5-dinitro-                                             phenyl]sulfonyl]-S,S-dimethyl-                                                 sulfilimine                                                      prosulfocarb  S-benzyldipropylthiocarbamate                                    prynachlor    2-chloro-N-(1-methyl-2-propynyl)-                                              acetanilide                                                      pyrazon       5-amino-4-chloro-2-phenyl-3(2H)-                                               pyridazinone                                                     pyrazosulfuron-                                                                              ethyl 5-[[[[(4,6-dimethoxy-2-                                    ethyl         pyrimidinyl)amino]carbonyl]-                                                   amino]sulfonyl]-1-methyl-1H-                                                   pyrazole-4-carboxylate                                           pyrazoxyfen   2-[[4-(2,4-dichlorobenzoyl)-                                                   1,3-dimethyl-1H-pyrazol-5-yl]-                                                 oxy]-1-phenylethanone                                            pyridate      O-(6-chloro-3-phenyl-4-pyrida-                                                 zinyl) S-octyl carbonothioate                                    quizalofop    (+)-2-[4-[(6-chloro-2-quinoxa-                                   ethyl         linyl)oxy]phenoxy]propanoic                                                    acid, ester                                                      secbumeton    N-ethyl-6-methoxy-N'-(1-methyl-                                                propyl)-1,3,5-triazine-2,4-                                                    diamine                                                          sethoxydim    2-[1-(ethoxyimino)butyl]-5-[2-                                                 (ethylthio)propyl]-3-hydroxy-                                                  2-cyclohexen-1-one                                               siduron       N-(2-methylcyclohexyl)-N'-phenyl-                                              urea                                                             simazine      6-chloro-N,N'-diethyl-1,3,5-                                                   triazine-2,4-diamine                                             simetryn      N,N'-diethyl-6-(methylthio)-1,3,5-                                             triazine-2,4-diamine                                             sodium chlorate                                                                              sodium chlorate                                                  sodium mono-  chloroacetic acid, sodium salt                                   chloroacetate                                                                  sulfometuron  2-[[[[(4,6-dimethyl-2-pyrimi-                                    methyl        dinyl)amino]carbonyl]amino]-                                                   sulfonyl]benzoic acid, methyl                                                  ester                                                            2,4,5-T       (2,4,5-trichlorophenoxy)acetic                                                 acid                                                             2,3,6-TBA     2,3,6-trichlorobenzoic acid                                      TCA           trichloroacetic acid                                             tebutam       2,2-dimethyl-N-(1-methylethyl)-N-                                              (phenylmethyl)propanamide                                        tebuthiuron   N-[5-(1,1-dimethylethyl)-1,3,4-                                                thiadiazol-2-yl]-N,N'-dimethyl-                                                urea                                                             terbacil      5-chloro-3-(1,1-dimethylethyl)-6-                                              methyl-2,4(1H,3H)-pyrimidine-                                                  dione                                                            terbuchlor    N-(butoxymethyl)-2-chloro-N-[2-                                                (1,1-dimethylethyl)-6-methyl-                                                  phenyl]acetamide                                                 terbumeton    N-(1,1-dimethylethyl)-N'-ethyl-                                                6-methoxy-1,3,5-triazine-                                                      2,4-diamine                                                      terbuthyl-    2-(tert-butylamino)-4-chloro-6-                                  azine         (ethylamino)-s-triazine                                          terbutol      2,6-di-tert-butyl-p-tolyl                                                      methylcarbamate                                                  terbutryn     N-(1,1-dimethylethyl)-N'-ethyl-                                                6-(methylthio)-1,3,5-triazine-                                                 2,4-diamine                                                      thifensulfuron                                                                               3-[[[[(4-methoxy-6-methyl-                                                     1,3,5,triazin-2-yl)amino]-                                                     carbonyl]amino]sulfonyl]-                                                      2-thiophenecarboxylic acid,                                                    methyl ester                                                     thiameturon-  methyl 3-[[[[(4-methoxy-6-                                       methyl        methyl-1,3,5-triazin-2-yl)-                                                    amino]carbonyl]amino]-                                                         sulfonyl]2-thiophenecarboxylate                                  thiazafluron  N,N'-dimethyl-N-[5-(trifluoro-                                                 methyl)-1,3,4-thiadiazol-                                                      2-yl]urea                                                        thiobencarb   S-[(4-chlorophenyl)methyl]-                                                    diethylcarbamothioate                                            tiocarbazil   S-(phenylmethyl) bis(1-methyl-                                                 propyl)carbamothioate                                            tralkoxydim   2-[1-(ethoxyimino)propyl]-3-                                                   hydroxy-5-(2,4,6-trimethyl-                                                    phenyl)-2-cyclohexen-1-one                                       triallate     S-(2,3,3-trichloro-2-propenyl)-                                                bis(1-methylethyl)carbamothioate                                 triasulfuron  2-(2-chloroethoxy)-N-[[(4-methoxy-                                             6-methyl-1,3,5-triazin-2-yl)-                                                  amino]carbonyl]benzene-                                                        sulfonamide                                                      tribenuron    2-[[[[N-(4-methoxy-6-methyl-1,3,5-                               methyl        triazine-2-yl)-N-methylamino]-                                                 carbonyl]amino]sulfonyl]benzoic                                                acid, methyl ester                                               triclopyr     [(3,5,6-trichloro-2-pyridinyl)-                                                oxy]acetic acid                                                  *tridiphane   (+)2-(3,5-dichlorophenyl)-2-                                                   (2,2,2-trichloroethyl)oxirane                                    trietazine    6-chloro-N,N,N'-triethyl-1,3,5-                                                triazine-2,4-diamine                                             trifluralin   2,6-dinitro-N,N-dipropyl-4-(tri-                                               fluoromethyl)benzenamine                                         trimeturon    1-(p-chlorophenyl)-2,3,3-tri-                                                  methylpseudourea                                                 2,4-D         (2,4-dichlorophenoxy)acetic acid                                 2,4-DB        4-(2,4-dichlorophenoxy)butanoic                                                acid                                                             vernolate     S-propyl dipropylcarbamothioate                                  xylachlor     2-chloro-N-(2,3-dimethylphenyl)-N-                                             (1-methylethyl)acetamide                                         ______________________________________                                    

Selective herbicidal properties of the subject compounds were discovered in greenhouse tests as described below.

                                      TABLE OF COMPOUNDS                           __________________________________________________________________________      ##STR28##                                                                     COMPOUND                                                                               R.sup.3                                                                           Y  Z       O       n m.p. (°C.)                              __________________________________________________________________________     1       CF.sub.3                                                                          CH CH      COCH.sub.2 CF.sub.3                                                                    0 oil                                            2       CF.sub.3                                                                          N  COCH.sub.2 CF.sub.3                                                                    CH      0 114-117                                        3       CF.sub.3                                                                          N  COMe    CH      0 141-142                                        4       CF.sub.3                                                                          N  CH      COMe    0 119-121                                        5       CF.sub.3                                                                          N  N       COCH.sub.2 CF.sub.3                                                                    1 168-169                                        6       CF.sub.3                                                                          N  N       COCH.sub.2 CF.sub.3                                                                    0 140-141                                        7       CF.sub.3                                                                          N  CH      COCH.sub.2 CF.sub.3                                                                    0 46-48                                          8       CF.sub.3                                                                          N  CCF.sub.3                                                                              CH      0 93-94                                          9       CF.sub.3                                                                          N  CH      CCF.sub.3                                                                              0 117-118                                        10      CF.sub.3                                                                          N  N       COCHF.sub.2                                                                            1 128-129                                        11      CF.sub.3                                                                          N  N       COCHF.sub.2                                                                            0 109-110                                        12      CF.sub.3                                                                          N  N       COMe    1 147-148                                        13      CF.sub.3                                                                          N  N       COMe    0 117-118                                        14      CF.sub.3                                                                          N  COCHF.sub.2                                                                            CH      0 105-106                                        15      CF.sub.3                                                                          N  CH      COCHF.sub.2                                                                            0 103-104                                        16      CN N  CCF.sub.3                                                                              CH      0 165-166                                        17      CN N  CH      CCF.sub.3                                                                              0 171-172                                        __________________________________________________________________________

TEST A

Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-galli), blackgrass (Alopecurus myosuroides), cheatgrass (Bromus secalinus), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria spp.), bedstraw (Galium aparine), giant foxtail (Setaria faberii), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), rape (Brassica napus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulcaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avena fatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were also treated with postemergence applications of test chemicals. Plants ranged in height from two to eighteen cm (one to four leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (--) response means no test result.

                                      TABLE A                                      __________________________________________________________________________              COMPOUND                                                                       Rate (2000 g/ha)                                                                         Rate (400 g/ha)                                                      1 3 4  5  1 2 3 4  5  7 8  9  10 11 12 13 14 15 16 17                 __________________________________________________________________________     POST-                                                                          EMERGENCE                                                                      Barley   0 0 2  3  0 0 0 2  0  3 2  3  2  3  4  5  4  2      2                                                                       2                        Barnyardgrass                                                                           1 1 3  -- 0 2 1 1  -- 4 2  5  5  2  3  5  5  9      4                                                                       8                        Bedstraw 5 1 6  5  0 3 1 2  2  7 4  6  7  6  7  6  6  7      3                                                                       5                        Blackgrass                                                                              0 0 4  3  0 0 0 2  2  2 3  3  6  5  5  7  4  8      2                                                                       3                        Cheatgrass                                                                              0 0 2  2  0 1 0 1  0  2 0  2  5  4  5  6  2  4      1                                                                       2                        Chickweed                                                                               4 1 7  5  2 3 0 5  2  4 4  5  7  6  7  7  7  7      4                                                                       7                        Cocklebur                                                                               5 2 8  -- 2 4 2 4  -- --                                                                               -- -- -- -- -- -- 7  8      3                                                                       --                       Corn     0 2 1  2  0 1 0 1  2  1 2  2  3  2  2  2  3  5      2                                                                       2                        Cotton   8 3 5  3  0 8 0 1  -- 2 2  3  8  4  5  6  3  9      5                                                                       8                        Crabgrass                                                                               --                                                                               1 2  2  --                                                                               1 1 2  1  2 3  6  5  4  4  3  4  9      2                                                                       7                        Giant foxtail                                                                           0 2 1  3  0 2 1 2  2  3 2  2  6  3  5  5  4  5      3                                                                       5                        Lambsquarters                                                                           4 6 6  8  3 5 2 4  4  9 3  9  6  7  8  7  10 10     10                                                                      10                       Morningglory                                                                            2 4 7  8  2 6 4 5  3  8 7  8  7  2  4  4  8  8      3                                                                       6                        Nutsedge 1 5 1  0  1 0 0 0  -- 1 -- 0  1  -- -- 2  2  7      --                                                                      0                        Rape     0 4 4  8  0 6 3 2  5  5 0  4  9  8  9  8  5  7      6                                                                       8                        Rice     1 0 1  1  1 0 0 1  1  1 0  1  2  1  2  1  2  3      1                                                                       2                        Sorghum  3 0 2  1  0 0 0 1  1  1 1  1  2  1  2  2  2  3      2                                                                       1                        Soybean  5 5 6  6  1 5 4 6  6  7 5  8  5  5  7  6  7  8      7                                                                       5                        Sugar beet                                                                              6 9 8  8  2 8 8 5  8  7 8  9  9  9  9  9  9  9      9                                                                       9                        Velvetleaf                                                                              1 0 3  2  1 3 0 1  3  6 2  2  7  3  4  5  7  8      1                                                                       1                        Wheat    0 0 0  1  0 0 0 0  0  3 2  2  2  4  3  4  3  3      0                                                                       3                        Wild buckwheat                                                                          2 1 2  3  2 3 2 1  1  2 3  3  6  8  7  6  7  7      4                                                                       6                        Wild oat 1 0 2  6  0 0 0 1  3  4 4  4  8  6  8  8  6  8      3                                                                       4                        __________________________________________________________________________                                COMPOUND                                                                       Rate (100 g/ha)                                                                2 6 7  8 9  10 11 12 13  14                                                                               15 16 17                 __________________________________________________________________________                       POST-                                                                          EMERGENCE                                                                      Barley   0 1 0  0 0  2  1  2  2  2  2  0  0                                    Barnyardgrass                                                                           1 2 2  1 2  2  2  3  1  2  4  2  3                                    Bedstraw 2 7 4  3 3  6  4  5  4  3  3  2  3                                    Blackgrass                                                                              0 2 2  2 2  3  2  2  4  4  2  2  2                                    Cheatgrass                                                                              1 2 0  0 0  3  1  2  3  2  2  1  0                                    Chickweed                                                                               3 7 5  2 4  5  3  5  3  5  5  4  7                                    Cocklebur                                                                               2 --                                                                               -- --                                                                               -- -- -- -- -- 5  2  2  --                                   Corn     1 1 1  1 1  2  1  2  2  1  3  1  2                                    Cotton   7 7 2  0 3  8  5  6  3  9  9  5  5                                    Crabgrass                                                                               1 2 1  2 4  4  2  3  2  3  7  2  3                                    Giant foxtail                                                                           1 2 1  1 1  3  1  4  2  2  3  2  3                                    Lambsquarters                                                                           3 5 4  2 4  5  3  5  5  9  10 6  10                                   Morningglory                                                                            3 3 6  2 5  5  3  2  2  6  2  3  5                                    Nutsedge 0 0 0  0 0  0  1  1  0  0  0  0  1                                    Rape     0 7 2  0 0  6  7  6  6  2  4  6  5                                    Rice     0 1 0  0 0  1  1  2  0  1  1  1  1                                    Sorghum  0 2 1  1 1  1  1  2  2  1  2  1  1                                    Soybean  4 5 4  3 7  4  4  4  6  3  7  5  6                                    Sugar beet                                                                              7 8 5  7 7  9  8  8  8  9  8  9  8                                    Velvetleaf                                                                              1 2 2  1 3  4  1  4  2  2  1  1  1                                    Wheat    0 2 0  0 0  3  1  1  2  2  2  0  0                                    Wild buckwheat                                                                          1 2 2  2 2  5  5  7  2  4  3  2  5                                    Wild oat 0 1 0  0 2  6  4  5  5  3  3  2  1                  __________________________________________________________________________              COMPOUND                                                                       Rate (2000 g/ha)                                                                         Rate (400 g/ha)                                                      1 3 4  5  1 2 3 4  5  7 8  9  10 11 12 13 14 15  16                                                                               17                 __________________________________________________________________________     PRE-                                                                           EMERGENCE                                                                      Barley   0  0                                                                               2  3  0 0 0 0  2   3                                                                               2  2  3  3  2  5  5  9      2                                                                       1                        Barnyardgrass                                                                           0  0                                                                               9  8  0 0 0 1  7   8                                                                               5  10 8  7  2  7  10 10     8                                                                       9                        Bedstraw 0  0                                                                               3  10 0 5 0 0  7   6                                                                               2  8  10 7  8  9  10 10     2                                                                       3                        Blackgrass                                                                              0  0                                                                               3  9  0 0 0 0  10  9                                                                               10 10 5  8  9  10 9  10     10                                                                      9                        Cheatgrass                                                                              0  0                                                                               4  9  0 0 0 2  9   4                                                                               8  10 5  8  7  10 9  10     4                                                                       6                        Chickweed                                                                               0  2                                                                               10 10 0 7 0 10 10  3                                                                               3  7  9  9  10 10 10 10     10                                                                      9                        Cocklebur                                                                               0 --                                                                               -- -- --                                                                               0 --                                                                               -- -- --                                                                               -- -- 2  4  1  2  5  5      2                                                                       0                        Corn     1  0                                                                               1  2  0 0 0 1  3   1                                                                               2  2  2  2  1  5  3  3      1                                                                       2                        Cotton   0  0                                                                               0  4  0 0 0 0  0   0                                                                               0  0  1  1  1  2  0  1      0                                                                       0                        Crabgrass                                                                               1  2                                                                               10 10 0 5 2 8  10 10                                                                               9  10 9  9  10 10 10 10     9                                                                       10                       Giant foxtail                                                                           1  5                                                                               10 10 0 6 2 7  10 10                                                                               10 10 10 9  10 10 10 10     10                                                                      10                       Lambsquarters                                                                           0 10                                                                               10 10 0 7 8 10 10  9                                                                               10 10 -- 10 -- 10 10 10     10                                                                      10                       Morningglory                                                                            0  0                                                                               3  8  0 0 0 0  5   1                                                                               1  5  5  5  2  5  5  6      1                                                                       2                        Nutsedge 6  0                                                                               -- 2  0 0 0 -- 0   0                                                                               0  3  -- 0  0  0  -- --     --                                                                      5                        Rape     0  0                                                                               2  6  0 1 0 0  7   3                                                                               2  2  10 7  4  10 6  10     2                                                                       2                        Rice     2  1                                                                               2  2  1 0 0 1  1   1                                                                               0  2  1  1  1  1  1  1      2                                                                       0                        Sorghum  0  0                                                                               2  2  0 0 0 1  1   1                                                                               10 3  2  1  1  5  2  2      2                                                                       1                        Soybean  0  0                                                                               2  1  0 0 0 0  0   0                                                                               0  1  2  1  2  2  1  2      1                                                                       0                        Sugar beet                                                                              0  0                                                                               9  10 0 2 0 2  9   7                                                                               8  8  10 9  7  10 10 10     9                                                                       9                        Velvetleaf                                                                              1  1                                                                               6  10 0 0 0 0  6   1                                                                               2  10 2  5  1  3  7  10     1                                                                       0                        Wheat    0  0                                                                               3  3  0 0 0 0  3   2                                                                               3  3  2  5  2  4  3  6      0                                                                       1                        Wild buckwheat                                                                          0  2                                                                               4  8  0 0 0 5  6   4                                                                               4  8  7  9  8  7  7  10     9                                                                       4                        Wild oat 0  2                                                                               8  9  0 2 0 4  9   9                                                                               9  9  7  8  9  9  10 10     6                                                                       9                        __________________________________________________________________________                                COMPOUND                                                                       Rate (100 g/ha)                                                                2 6 7  8 9  10 11 12 13 14 15 16 17                 __________________________________________________________________________                       PRE-                                                                           EMERGENCE                                                                      Barley   0 2 0  0 2  2  2  1  1  2  4  0  0                                    Barnyardgrass                                                                           0 2 3  1 4  4  4  1  5  3  10 2  3                                    Bedstraw 2 6 2  0 3  4  2  3  3  3  10 1  2                                    Blackgrass                                                                              0 6 8  7 9  5  5  5  4  6  10 0  3                                    Cheatgrass                                                                              0 7 2  3 9  6  4  3  5  6  10 0  2                                    Chickweed                                                                               0 8 0  0 2  6  3  5  8  2  10 0  7                                    Cocklebur                                                                               0 --                                                                               -- --                                                                               -- 0  -- 0  0  1  3  0  0                                    Corn     0 1 1  0 1  1  1  1  1  1  1  1  1                                    Cotton   0 0 0  0 0  0  0  0  1  0  0  0  0                                    Crabgrass                                                                               1 7 9  8 9  9  7  9  9  9  10 9  10                                   Giant foxtail                                                                           1 9 10 9 10 9  9  9  9  10 10 9  9                                    Lambsquarters                                                                           0 --                                                                               0  3 5  10 8  0  10 10 10 0  10                                   Morningglory                                                                            0 1 0  0 2  1  0  0  1  1  6  1  0                                    Nutsedge 0 0 0  --                                                                               -- 0  0  0  0  0  -- 0  0                                    Rape     0 2 2  0 0  1  1  1  7  1  6  0  0                                    Rice     0 0 0  0 0  0  0  0  0  0  1  0  0                                    Sorghum  0 1 1  0 0  1  1  0  1  0  1  0  1                                    Soybean  0 1 0  0 0  1  1  0  1  0  1  0  0                                    Sugar beet                                                                              0 4 4  4 7  8  7  5  6  9  9  8  7                                    Velvetleaf                                                                              0 0 0  0 1  0  1  0  1  1  3  0  0                                    Wheat    0 1 0  0 2  1  0  1  1  1  2  0  0                                    Wild buckwheat                                                                          0 7 0  2 2  5  7  0  2  5  9  2  0                                    Wild oat 0 4 3  4 9  5  4  4  8  8  8  2  3                  __________________________________________________________________________ 

What is claimed is:
 1. A compound of the formula ##STR29## wherein X is CH;Y is N; Z, CR⁴ or CR⁵ ; Q, CR⁴ or CR⁵ ; R is C₁ -C₄ alkyl, C₂ -C₄ alkoxyalkyl, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₃ alkylamino or N(C₁ -C₃ alkyl)(C₁ -C₃ alkyl); R¹ is H, F, Cl or CH₃ ; R² is H, halogen, C₁ -C₃ alkyl, C₁ -C₃ haloalkyl, C₁ -C₃ alkoxy or C₁ -C₃ haloalkoxy; R³ is H, halogen, C₁ -C₄ alkyl, C₂ -C₄ alkenyl, C₂ -C₄ alkynyl, C₁ -C₄ haloalkyl, C₃ -C₄ halocycloalkyl, C₂ -C₄ haloalkenyl, C₂ -C₄ haloalkynyl, OR⁶, S(O)_(n) R₇ or CN; R⁴ is H, CN, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or halogen; R⁵ is C₁ -C₄ haloalkyl, C₃ -C₅ halocycloalkyl, C₂ -C₄ haloalkenyl, C₂ -C₄ haloalkynyl, OR⁶, S(O)_(n) R⁷ or halogen; R⁶ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, C₃ -C₄ alkynyl, C₁ -C₄ haloalkyl, C₂ -C₄ haloalkenyl or C₂ -C₄ haloalkynyl; R⁷ is C₁ -C₂ alkyl or C₁ -C₂ haloalkyl; R⁸ is H, CN, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or halogen; and n is 0; 1 or 2;or their mono N-oxides or their agriculturally suitable salts, provided that: (a) when Z is CR⁴, then Q is CR⁵ ; and (b) when Q is CR⁴, then Z is CR⁵.
 2. The compounds of claim 1 whereinR¹ is H or F; and R² is H or F.
 3. The compounds of claim 2 whereinR³ is F, Cl, Br, C₁ -C₄ haloalkyl, OR⁶, S(O)_(n) R⁷ or CN; n is 0; Y is N; and their mono N-oxides.
 4. The compounds of claim 3 whereinR is C₁ -C₃ alkyl, C₂ -C₃ alkoxyalkyl, C₂ -C₃ alkenyl, C₂ -C₃ alkynyl, C₁ -C₂ alkoxy, C₁ -C₂ alkylthio, C₁ -C₂ alkylamino and N(C₁ -C₂ alkyl)(C₁ -C₂ alkyl); R⁶ is C₁ -C₃ alkyl, allyl, propargyl, C₁ -C₃ haloalkyl, C₂ -C₃ haloalkenyl.
 5. The compounds of claim 4 wherein Z is CH or C--CN.
 6. The compound of claim 1 which is:2-(difluoromethoxy)-6-methyl-8-[3-(trifluoromethyl)phenyl]quinoxaline.
 7. The compound of claim 1 which is:6-methyl-2-(trifluoromethyl)-8-[3-(trifluoromethyl)phenyl]quinoxaline.
 8. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 1 and at least one of the following: surfactant, solid or liquid diluent.
 9. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 2 and at least one of the following: surfactant, solid or liquid diluent.
 10. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 3 and at least one of the following: surfactant, solid or liquid diluent.
 11. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 4 and at least one of the following: surfactant, solid or liquid diluent.
 12. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 5 and at least one of the following: surfactant, solid or liquid diluent.
 13. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 6 and at least one of the following: surfactant, solid or liquid diluent.
 14. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 7 and at least one of the following: surfactant, solid or liquid diluent.
 15. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 1. 16. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 2. 17. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 3. 18. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 4. 19. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound, of claim
 5. 20. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 6. 21. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 7. 